JPH049141B2 - - Google Patents

Abstract

A novel composite comprises a substrate having a coating matrix including an initial layer of a perfluoropolymer and an overcoat comprising a fluoroelastomer, a fluoroplastic, a fluoroelastomer/fluoroplastic blend, or a combination thereof. The perfluoropolymer in the initial layer may be a perfluoroplastic, a perfluoroelastomer, or blends thereof. In a separate embodiment, the novel composite includes a substrate coated solely with one or more layers of perfluoroelastomer alone or as a blend with a perfluoroplastic. Where the substrate is not susceptible to hydrogen fluoride corrosion, the composite may include solely one or more layers of a blend of a fluoroelastomer and a hydrogen-containing perfluoroplastic. Cross-linking accelerators may be used to cross-link one or more of the resins contained in the coating layers. Each composite may be topcoated with the layer or layers of a fluoroplastic, fluoroelastomer, and/or a blend thereof. The composite is flexible, exhibits good matrix cohesion and possesses substantial adhesion of the matrix to the material acting as the reinforcement or substrate. A method for making such a composite comprises the unique deployment of a perfluoropolymer directly onto the substrate in a relatively small amount sufficient to protect the substrate from chemical corrosion without impairing flexibility, followed by the application of the overcoat layer.

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to new and useful fluoropolymer composite materials that include coated substrates. In particular, the present invention provides novel coatings useful as coatings in the production of reinforced woven composite materials that are flexible and exhibit good matrix integrity, and in which the coating matrix exhibits good adhesion or bonding to the substrate. fluoroelastomer/fluoroplastic matrix. The present invention includes composite materials that also have unusual chemical resistance, particularly in high temperature and high humidity environments. The present invention provides a method for making such composite materials that combines the desirable high temperature, chemical inertness of fluoroplastic materials with the desirable mechanical properties of fluoroelastomers in a manner that maintains desirable cloth-like flexibility. Also related. Perhaps the best-known subclass of fluoropolymers exhibits excellent electrical and physical properties such as low coefficient of friction, low surface free energy (i.e., does not leak into many organic fluids), and extremely high hydrophobicity. It is a substance called "perfluoroplastic" which is generally recognized to contain Fluoroplastics, especially perfluoroplastics (i.e. hydrogen-free fluoroplastics) such as polytetrafluoroethylene (PTFE), fluoro(ethylene-propylene) copolymer (FEP), copolymer of tetrafluoroethylene and perfluoropropyl vinyl ether (PFA) is particularly useful in a variety of industrial and domestic applications because it is resistant to a wide range of chemicals even at high temperatures. However, these fluoroplastics are partially crystalline, so
They exhibit a degree of stiffness or lack of compliance, which is detrimental to the utilization of these desirable properties. This disadvantage is particularly noticeable and undesirable in reinforced composite materials where some degree of flexibility and/or elasticity and/or conformability is required. The broad class of fluoropolymers also includes materials called "fluoroelastomers" that are not only elastomers, but also, to a lesser extent, have the physical and electrical properties described above of fluoroplastics. Fluoroelastomers, including perfluoroelastomers, have low bending modulus and conformability that fluoroplastics lack. However, hydrogen-containing fluoroelastomers do not retain the other advantageous properties associated with fluoropolymers over a wide temperature range or at such high levels as perfluoroplasts. In other words, perfluoroplastics simply perform better over a wider temperature range. Additionally, hydrogen-containing fluoroelastomers (i.e., partially fluorinated fluoroelastomers) generally contain
It decomposes rapidly at high temperatures, resulting in not only a loss of physical integrity but also the formation of hydrofluoric acid. Of course, hydrofluoric acid can be used with most materials, including those commonly used as reinforcing substrates in textile composites.
It is particularly corrosive to glass fibers. For this reason, hydrogen-containing fluoroelastomer-based composite materials currently used in high temperature environments must be replaced relatively frequently. Despite these drawbacks, hydrogen-containing fluoroelastomers
It is considered an excellent candidate for a variety of commercial applications requiring a lower bending modulus than that of stiffer fluoroplastics. In this regard, attempts have been made to use reinforced fluoroelastomer composites where good thermochemical and mechanical properties at high temperatures, i.e., low modulus, are required. One such application is high temperature expansion joints connecting large duct sections in applications such as power plant systems. These ducts have, in the past, been essentially chemically and thermally robust at the ends of their sections, and have been designed to withstand temperatures up to 286.7°C (550〓) or 342.2°C.
They were joined by a metal bellows that provided the lowest thermomechanical shock resistance under normal operating conditions, which can include temperatures up to (650〓). In an effort to improve the mechanical properties of metal expansion joints, where the flexibility of industrial garments is desirable, fabric composites coated with fluoroelastomer-based rubber compounds have been used. These fabric composites are fluoroelastomer compositions based on copolymers of hexafluoropropylene (HFP) and vinylidene fluoride (VF ₂ ) or terpolymers containing HFP, VF ₂ and tetrafluoroethylene (TFE). Various reinforcement materials were used, including woven glass fibers coated with matrices containing . The fluoroelastomer materials used all contain at least some hydrogen and as such have drawbacks with respect to hydrofluoric acid elimination. Additionally, prior art fluoropolymers
In order for composite materials to be useful at high temperatures, they typically include a relatively viscous matrix of fluoroelastomer-based rubber, resulting in
Increased stiffness, potentially exacerbating problems arising from hydrofluoric acid formation and thermal embrittlement. In an effort to avoid these problems, composite materials using hydrogen-containing fluoroelastomer compounds, acid-resistant alloys such as INCONEL, or high temperature synthetic materials such as NOMEX and KEVLAR have been developed. It is reinforced with things. However, none of these composite materials provides the desired combination of heat resistance, chemical resistance, and acceptable matrix integrity. Westley U.S. Patent No.
Even when a chemically resistant substrate such as polytetrafluoroethylene (PTFE) is coated with a fluoropolymer as in No. 3513064, the resulting composite material is
Composite materials have the property of being used only in certain narrow applications, as they can only be obtained through the selection of specific coating materials that are limited by processing conditions. In an effort to obtain an improved balance of fluoropolymer properties, attempts have been made in the prior art to combine the respective favorable properties of fluoroplastic and fluoroelastomer materials in the manufacture of coated fabrics. However, the blends obtained in these attempts were particularly difficult to achieve at high temperatures, e.g.
(500〓) At higher temperatures, one obtains a combination of unfavorable properties of the components or shows a decrease in favorable properties. A typical example of these prior art efforts can be found in Robb, US Pat. No. 3,019,206. Perfluoropolymers, whether thermoplastic or elastomeric, have excellent heat and chemical resistance, but their low surface free energy and chemical inertness make them highly resistant to both themselves and other materials. It is difficult to create a durable bond between materials. This difficulty is usually alleviated by roughening the surface, such as using inorganic fillers or abrasive surfaces, to promote mechanical bonding. Special surface treatments can also be used, such as surface treatments based on chemical etching. However, none of these known techniques provides a bond that is particularly strong or durable under environmental stresses such as UV- or heat-induced oxidation. It is therefore an object of the present invention to provide a fluoropolymer composite comprising a substrate coated with a fluoroelastomer/fluoroplastic matrix. The composite materials of the present invention are flexible, exhibit good matrix cohesion, and have excellent adhesion between the matrix and the material acting as reinforcement or substrate, as well as excellent high-temperature adhesion of fluoroplastics when desired. It retains the low stiffness associated with fluoroelastomers combined with performance. Another object of the present invention is to provide hydrogen-containing fluoroelastomer-based materials that are relatively lightweight, strong, and chemically and thermally superior, especially under high temperature and high humidity conditions. It is an object of the present invention to provide a fluoropolymer composite material that improves the problem of polymer degradation that previously occurred in the use of composite materials with coating matrices. Yet another object of the present invention is to provide fluoropolymer composites with outstanding chemical properties for use as chemical liners, expansion joints and life safety equipment such as escape hoods, escape chutes, chemical resistant protective clothing. The goal is to provide materials. Yet another object of the present invention is that it can be used to manufacture superior plied structures, including multiple biased-plied composites, as well as composites with a single coated surface. It is an object of the present invention to provide a composite material having the combined benefits of perfluoroplastics and fluoroelastomers. According to the invention, a graded application of the fluoropolymer layer is carried out to form a coating matrix for application to a substrate in the production of the novel composite material. The fluoropolymer layer is
It can include perfluoropolymers as well as hydrogen-containing fluoropolymer components that are developed in novel and unique ways to combine the advantageous properties of each of the different fluoropolymer components as desired. Hydrogen-containing fluoropolymer components include fluoroplasts, fluoroelastomers, and blends of fluoroelastomers and fluoroplasts. The perfluoropolymer component(s) may be first applied to provide a hydrogen-free interface that would otherwise make the hydrogen-containing fluoropolymer component susceptible to the potentially corrosive effects of generated hydrogen fluoride. Certain substrate materials are shielded from such effects while preserving the basic flexibility of the substrate. It is also possible for the fluoroplastic component to constitute the topcoat or surface layer, or a portion thereof, if thermocoatable rather than elastomeric behavior is desired. The hydrogen-containing fluoroelastomer component is contained within the coating matrix such that it is separated by the perfluoropolymer layer from the substrate potentially susceptible to hydrogen fluoride corrosion, yet enhances the flexibility of the resulting composite membrane. used for. When used as or within a topcoat or surface coat, the fluoroelastomer component serves to enhance the compliance of the composite material and generally impart rubbery properties to the surface. The novel reinforced composite material of the present invention comprises: (A) a perfluoropolymer, most preferably a perfluoroplastic such as polytetrafluoroethylene (PTFE) or a perfluoroelastomer such as KALREZ (Dupont) or blends thereof; (B) (1) a fluoroelastomer or perfluoroelastomer; and/or (2) a fluoroplastic or perfluoroplastic;
and/or (3) a blend of () a fluoroelastomer or perfluoroelastomer and () a fluoroplastic, preferably a perfluoroplastic such as polytetrafluoroethylene (PTFE), wherein the fluoroelastomer or perfluoroelastomer is about 10-90% by weight, preferably about
It comprises a substrate, preferably a textile substrate, coated on one or both sides with a matrix having one or more overcoating layers of the blend comprising 25-60% by weight. In an embodiment of the present invention, the basic coating matrix comprises Elements A and B as described above, all with multiple fluoropolymer coating layers strategically used to obtain the desired properties. In embodiments where only one side of the substrate is coated with the matrix, the other side of the substrate can be adhered to another substrate. Each composite material of the invention comprises one or two layers of a fluoroelastomer and/or a fluoroplastic and/or a blend of a fluoroplastic and a fluoroelastomer (which may differ in composition from the blend of the overcoat layer). Can be top coated in more than one layer. Furthermore, the resin contained in the coating layer can be prepared using relatively small amounts of cross-linking promoters such as triallylisocyanurate, triallylimidazole, etc., optionally by the use of high-energy electrons or actinic radiation. One or more of these can be bridged. In accordance with various embodiments of the present invention, the composite materials produced are characterized by good matrix cohesion and good adhesion between the substrate and the fluoropolymer matrix. Composite materials can also be produced with extraordinary resistance to thermal and chemical degradation and accommodation to thermomechanical shock. The composite materials of the present invention require less coverage or less layer thickness than similar composite materials of the prior art, resulting in a lighter weight and/or thinner yet stronger product. Any suitable reinforcing material that can withstand processing temperatures can be used as the substrate. Examples of reinforcing materials include:
In particular, glass, glass fiber, ceramic, graphite (carbon), PBI (polybenzimidazole),
PTFE, polyalamides such as KEVLAR and NOMEX, metal wires, HORIEFIRE such as TYVEK, polyesters such as REEMAY, polyamides, polyimides, novoloid phenolic fibers, KYNAR ), TEFZEL, KYNOL, thermo-plastics, polyethersulfones, polyetherimides, polyetherketones, cotton, fabrics, and other natural and synthetic textile materials. The substrate can be a yarn or filament or monofilament or other fibrous material collected as such or as a fabric, or a woven material, a non-woven material, a knitted material, a mat-like material,
It can also be made of felt material or the like. Depending on the nature of the substrate and the intended end use of the composite,
The reinforcement or substrate is first or simultaneously impregnated with a suitable lubricant or impregnation, such as methylphenyl silicone oil, graphite, highly fluorinated fluids such as FLUOROLUBE or KRYTOX. It can be impregnated with a saturant and contain a coupling agent. The lubricant or impregnant serves three functions for the reinforcing substrate: (1) As a lubricant, it protects the substrate from self-wear by preserving the mobility of the reinforcing elements, and (2) As an impregnating agent, the primary polymer can reduce flexibility. (3) Retain in the substrate to inhibit extensive penetration of the coat into the substrate and (3) inhibit wicking of moisture or other degrading chemicals into the substrate in the finished product. The lubricant or impregnant may be applied separately as a first pass or in combination with the first application of the perfluoropolymer component. The present invention is particularly designed to minimize the deleterious effects of hydrogen fluoride produced by hydrogen-containing fluoroelastomer or fluoroplastic components and to retain good overall composite flexibility. Also contemplated is a novel method of manufacturing the composite material of the present invention which provides a unique development of the various coating layers, including the matrix. The method of the present invention, as it is,
Improved products with low stiffness modulus and good chemical resistance can be provided that are applicable over a wide temperature range for various end uses. The initial layer, described as Element A above, is applied to minimize stiffness of the final composite and maximize adhesion of the matrix to the substrate. The application of layer A can be carried out in one pass or in two or more passes, and preferably the openings in the aggregate substrate are intended for an additional overcoat layer or layers, especially with element B. In some cases, it remains substantially free to enhance flexibility. If the substrate used is a assembled fiber material, applying a first coating layer to the elements of the material (e.g. filaments or yarns), e.g. by dip coating or impregnation or extrusion coating, before collecting the fiber material. I can do it. Such materials can then be collected by weaving, knitting, felting, matting, etc. In embodiments that include both a hydrogen-containing fluoropolymer and a chemically susceptible substrate, such as a hydrogen fluoride susceptible substrate, the initial layer of perfluoropolymer encounters a reinforcing substrate, particularly a glass fiber substrate. It must be sufficient to provide substantial protection from possible chemicals such as hydrogen fluoride.
Again, depending on the substrate, an additional thin perfluoropolymer layer can be applied to ensure that the reinforcement has a sufficient protective layer. Proper selection, application, and deployment of the coating layer retains flexibility while providing a protective hydrogen-free perfluoropolymer interface that impedes the penetration of aggressive chemicals such as hydrogen fluoride. The initial coating layer is then coated with one or more layers of fluoroplast or fluoroelastomer or fluoroelastomer/fluoroplastic blend or combinations thereof, such as Part B above. Preferably, this portion of the matrix may include one or more layers of a blend containing fluoroelastomers in proportions to provide the desired balance of fluoropolymer properties in the composite. For example, if it is desired to have more pronounced elastomeric properties, blends with increased proportions of fluoroelastomer are used. The combination of layers A and B, in particular by using the fluoroelastomer/fluoroplastic blend according to the invention, can promote adhesion without prior physical or chemical treatment of the substrate or of the individual matrix layers. It has been found that sufficient cohesion within the matrix itself as well as matrix-substrate adhesion can often be obtained by thermal means alone, without the use of agents. The use of the matrices of the present invention and the special development of each matrix layer relative to each other and to the substrate by the method of the present invention provides sufficient flexibility while retaining the flexibility and desired properties of the different fluoropolymer components of the matrix. The ability to maintain a high degree of adhesion is obtained. This same feature allows the selection of a topcoat or surface layer with a fluoroplastic or fluoroelastomer or combination thereof contribution as desired. Thus, once the initial layer and topcoat layer have been developed, a topcoat of fluoroplastic or additional fluoroelastomer layer can be subsequently applied. Perfluoroplastics like polytetrafluoroethylene (PTFE) or perfluorolastomers like KALREZ or Concannon
Surface coats of fluoropolymer blend coatings comprising copolymers of perfluorinated vinyl ethers as described in U.S. Pat. give sex. The coating layer of the matrix of the invention can be applied by dip coating from an aqueous dispersion, but can be applied by any conventional method such as spraying, dipping and flow coating from an aqueous or solvent dispersion, as well as calendering, lamination, etc. The coating layer can be formed as is known in the art. As used herein, the term "fluoroplastic" is intended to include both hydrogen-containing fluoroplastics and hydrogen-free perfluoroplastics, unless otherwise specified. Fluoroplastics refers to polymers of general paraffin structure in which some or all of the hydrogens are replaced by fluorine, especially polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP) copolymers, perfluoroalkokenes (PFA) ) resins, polychlorotrifluoroethylene (PCTFE) and its copolymers with TFE or VF ₂ , ethylene-chlorotrifluoroethylene (BCTFE) copolymers and their modified products, ethylene-tetrafluoroethylene (ETFE) copolymers and their modified products , polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). Similarly, as used herein, the term "fluoroelastomer" refers to
It is intended to include both hydrogen-containing fluoroelastomers and hydrogen-free perfluoroelastomers.
Fluoroelastomers are polymers with elastomeric behavior, i.e. highly malleable, containing one or more fluorinated monomers with ethylenic unsaturation, such as vinylidene fluoride, and optionally one or more monomers containing ethylenic unsaturation. and other compounds. The fluorinated monomers are perfluorinated monoolefins, such as hexafluoropropylene or tetrafluoroethylene, or partially fluorinated monoolefins, which may contain other substituents, such as chlorine or perfluoroalkokenes,
For example vinylidene fluoride, pentafluoropropylene, chlorotetrafluoroethyl and perfluoroalkyl vinyl ethers such as perfluoro(methyl vinyl ether) or (propyl vinyl ether), the monoolefins preferably having terminal ethylenic double bonds. It is a straight chain or branched chain compound. Such other monomers include, for example, olefins with terminal ethylenic double bonds, especially ethylene, propylene. Elastomers are typically made of carbon, hydrogen,
Consists of oxygen and fluorine atoms. The fluoropolymer component can contain functional groups such as carboxyl, sulfonic acids and their salts, halogens, and reactive hydrogens on alkyl side chains. Preferred elastomers are copolymers of vinylidene fluoride and at least one other fluorinated monomer, especially one or more of hexafluoropropylene, pentafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene. Effective fluoroelastomers include copolymers of vinylidene fluoride and hexafluoroethylene, and VITON from DuPont.
These include terpolymers of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene, which are sold as FULOREL by 3M and DAIEL by Daiken. In addition, an elastomeric copolymer of vinylidene fluoride and chlorotrifluoroethylene is available from 3M as Kel-F.
It is sold as (Kel-F). Tetrafluoroethylene (TFE) manufactured by Asahi
Also contemplated is the use of AFLAS, a copolymer with and propylene. Preferred perfluoroelastomers include tetrafluoroethylene and hexafluoropropylene or Included are elastomeric copolymers with perfluoroalkyl comonomers, such as perfluoro(alkyl vinyl ether) comonomers, where R _f is a perfluoroalkyl or perfluoro(cyclo-oxaalkyl) moiety. Particularly preferred are those in which R _f is −CF ₃ or −C ₃ F ₇ or or (where n=1-4, X=H or Na or K
or F).
Particularly contemplated is KALREZ, a copolymer comprising TFE and perfluoromethyl vinyl ether (PMVE). If desired, and as known in the art, pigments,
Fillers or additives may be present in the matrix composition, such as plasticizers, stabilizers, softeners, extenders, and the like. For example, materials such as graphite, carbon black, titanium dioxide, alumina, alumina trihydrate, glass fibers, beads or microballoons, carbon fibers, magnesia, silica, asbestos, wollastonite, mica, etc. can be present. . The deployment of the various matrix layers on the substrate according to the invention is accomplished by a method consisting essentially of the following steps. 1. If necessary or desired, removal of size or finish from the substrate material, for example by thermal cleaning of the substrate in the case of woven glass fibers or by scouring of woven synthetic fabrics. 2. Applying a perfluoropolymer, preferably a perfluoroplastic such as PTFE or a perfluoroelastomer such as KALREZ or a blend thereof, as an initial layer to one or both sides of the substrate. As previously recognized, in one embodiment of the invention, a composite material is produced by simply applying one or more layers of perfluoroelastomers or blends thereof to a substrate as previously described. be able to. As previously mentioned, a suitable impregnant or lubricant, preferably methylphenyl silicone oil, is applied to the substrate either initially or simultaneously with the perfluoropolymer, typically in a mixture containing 2-14 parts by weight of lubricant. It can also be painted. If sufficient flexibility otherwise exists, a coupling agent can be used, if desired, to enhance adhesion of the matrix to the substrate. As previously described, the initial coating layer is applied to minimize the stiffness of the composite material, allowing for relatively lightweight applications depending on the weight and aperture of the substrate. As previously mentioned, if only one side of the substrate is coated, the other side of the substrate can be adhered to a different substrate material. 3. Applying to the initial layer one or more layers of a fluoroplast or a fluoroelastomer or a blend of a fluoroelastomer and a fluoroplast, preferably a perfluoroplast such as PTFE, or any combination thereof, as an overcoat. When a fluoroelastomer/fluoroplastic blend is used alone or as a layer over a fluoroelastomer layer, the blend should contain about 10-90% by weight, preferably 25-60% by weight of the fluoroelastomer component. . 4. If desired, a top coat of a fluoroplastic, also preferably a perfluoroplastic such as PTFE or a melt-manufacturable copolymer thereof, or an additional layer of a fluoroelastomer, preferably a perfluoroelastomer or a fluoroelastomer/fluoroplastic blend. The process of applying top coat. 5. Optionally, thicker fluoroplastic surface coatings by extrusion or lamination with melt processable films such as PTFE or FEP or PFA or fluoroelastomers such as VITON or AFLAS or KALREZ. The process of applying layers. Furthermore, it is clearly an advantage that the composite materials of the invention can be produced by aqueous dispersion techniques, if desired. The method of the invention can be carried out under conditions in which the cohesiveness of the matrix and its adhesion to the substrate are achieved thermally. One preferred method of manufacturing the composite materials of the invention is to first apply the perfluoropolymer from a latex or dispersion onto a suitably prepared substrate at a temperature conducive to fusing or solidifying the applied polymer. This includes the step of After this initial coating, a topcoat layer comprising a fluoroelastomer or fluoroplastic or a blend of a fluoroelastomer and a fluoroplastic derived from a latex or dispersion blend is applied such that the coating layer is dried, but not exposed to the heat of the coating layer. Apply in a manner that does not exceed the upper temperature limit of the most unstable component. The resulting partially consolidated coating layer is then subjected to a milder heat treatment under pressure,
Further hardens or strengthens the applied coating layer. Calendering is one convenient way to achieve this result. The topcoat is then applied at the required temperature to melt the highest melting point components for complete consolidation with minimal heat exposure of the most heat sensitive components. Latex is often useful for this operation. Optionally, a top coating layer can be applied by extrusion coating or calendering or lamination of the polymeric component onto the already consolidated coating layer. If a foamed topcoat is desired, extrusion coating is most preferred. In any embodiment of the invention, the top or surface layer can be applied as a foam to increase compressibility or to increase thickness at a lower density. During the manufacturing process of the matrix composition, the following additives can be included. Surfactants such as anionic or nonionic actives; creaming agents such as sodium alginate or ammonium alginate; viscosity modifiers or thickeners such as methylcellulose or ethylcellulose; fluorinated alkyl carboxylic acids or organic solvents or sulfones A lubricant such as an acid; or a film forming agent. The achievement of the remarkable properties of the composite material of the invention will be further explained and illustrated below with reference to the accompanying drawings. In FIG. 1, a pre-assembled (woven) yarn 10, which is first treated with silicone oil, is coated with a first coat of fluoropolymer that completely covers both the warp 14 and weft 16 of the yarn 10. Cover with layer 12. Layer 12 is then replaced by an overcoat layer 18 consisting of a blend of fluoroelastomer and fluoroplastic.
Cover with The resulting composite material can be further coated with an optional fluoroplastic or fluoroelastomer topcoat 20 as shown. FIG. 1A shows a side cross-sectional view of a woven composite material in which a coating layer 12 is applied to the yarns prior to assembly (weaving), completely surrounding and covering the yarns 10. Such composite materials can have enhanced flexibility due to the nature of the covering layer 12. FIG. 2 shows the development of the various layers of a coating matrix according to one embodiment of the invention, where the substrate is a woven substrate. An enlarged cross section of a plain woven substrate is shown in which both the warp 14 and weft 16 of yarn 10 are initially coated with a lightweight layer 22 of lubricant (not shown) and fluoropolymer. Layer 22 is yarn 1
0, but the openings 24 in the woven substrate
are shown in such a way that they remain free and clean and do not substantially reduce the overall flexibility of the final composite. This first coated substrate is then coated with a fluoroelastomer/fluoroplastic blend topcoat layer 26 according to the invention, and the warp threads 14
and the yarns 10, including the wefts 16, and the apertures 24, when coated with a more elastic blend layer 26, gives the resulting composite material a lower bending modulus. The invention and its advantages will also be illustrated by the following examples. The examples illustrate composite materials using various substrates and coating matrices contemplated by the present invention. Test methods for physical and chemical testing and property determination of composite materials produced according to the invention and controls are presented below.

【table】

【table】

[Table] Example 1 According to a preferred embodiment of the present invention,
An 18 oz/yd ² glass fiber substrate, Chemfab Model No. 15227, was heat cleaned to remove residual size. Next, the surface of this substrate was coated with PTFE [RE-3313, obtained as an aqueous dispersion with a solids content of 60% from DuPont] and methylphenyl silicone oil [ET-4327, obtained from Dow Corning]. 35% solids from company
[obtained as an aqueous emulsion]] was applied by immersion until the drying zone temperature was approximately
-350〓 and baking or sintering temperature is 700〓2
Dry and fuse in a zone coating tower. The coating layer is
It contained 93 parts PTFE and 7 parts methylphenyl silicone. This mixture was applied as a very light basecoat layer of 5 oz/yd ² to avoid undesirable stiffness. Only the threads in the substrate were covered, leaving the window open. From a blend of VITON B fluoroelastomer (VTR-5307, available as a 60-65% solids terpolymer latex from DuPont) and PTFE (TE-3313).
A total of about 20 oz/yd ² of the second coating layer was applied. This coating layer is applied by dipping in several passes, with a drying temperature of 200-350°C and a baking zone temperature of only 500°C.
Drying and baking were carried out in a two-zone tower. This blend (designated FMK-4-10-B) consisted of 60% by weight PTFE and 40% by weight terpolymer fluoroelastomer. The material was completed by calendering the coated fabric in a 300° calender, passing it through a coating tower with a final drying pass, and fusing or sintering the coating layer in a baking zone of 700°. Example 2 A thermally cleaned glass cloth substrate (Chemfab model no.
122, 32oz/yd ² ], the same primer coat composition as Example 1 at a weight of 40-41oz/yd ² and the same blend as Example 1 at a weight of 54-56oz/yd 2 .
A weight of yd ² was used to produce the composite material. moreover,
A top coat of PTFE was applied in several passes with TE-3313, reducing the total composite weight to approximately 60-62 oz/yd ²
I made it. In this example, the PTFE top coat is
After application of the blend, it was applied by dipping without prior calendering, dried and baked at 590°. The resulting material was calendered, passed through a tower, and treated at a baking temperature of 700° to sinter or fuse the coating layer. The so-called dry fused composite was given a final coat of PTFE by dipping in TE-3313, drying and fusing at 700°. This composite material has a thickness of 0.45″ and a warp/weft tensile strength of 1400/1375 lbs/in bend-fold of 1400/in.
1356lbs/in (warp/weft), tear strength 231/in
It was 295lbs/in (warp/weft). The coating adhesion is
231lbs/in and porosity is 0.013SCF/hr/ft ²
It was hot. Four additional composites were made according to the method of Example 2 using lighter weight glass cloth reinforcements and proportionally lighter cumulative layers of various matrix components as shown in the following table.

[Table] The test results of these composite materials are shown in Table 1 below.

【table】

[Table] Furthermore, Example 2A was applied to the expansion joint of the power plant.
Tested after 9 months of operation. The service degradation of this material was much lower than conventional fittings based on fluoroelastomers. Examples 3-8 Six additional composites were prepared following the methods of Examples 1 and 2, but varying the ratio of fluoroelastomer/PTFE blends as described below.

[Table] * Parts by weight of ingredients used at the concentration supplied by the manufacturer
** Parts by weight of ingredients when supplied as ingredients Test results for these compositions are shown in Table 3 below.

【table】

Table: Control Preparation A Control A composite was prepared using Chenfab model 15227 glass cloth (18 oz/yd ² ) that was thermally cleaned to remove residual size. This substrate is made of (a) fluoroelastomer (L-
80/20 (PRFE/
Fluoroelastomer) weight ratio blend
Coated to 41oz/ ^yd2 . This coating layer was processed in several passes at a processing temperature of 400°. Control B is simply a portion of Control A baked under dry fusing conditions like the composite of the present invention. Also, control C
Approx.
A portion of Control B with an amount of 1.25oz/ ^yd2 . The results of the physical tests for these controls are shown in Table 4.

[Table] * Extremely poor seal; coating layer squeezed out from joint.
Examples 9A-C Comparisons were made using samples of composite materials made according to Examples 1 and 2 but using different commercially available fluoroelastomers. The first composite material 9A is
It was made essentially the same as the composite of Example 6. Composite material 9B is essentially the same, but with L
-6517 fluoroelastomer (3M copolymer latex, 55% solids) was substituted.
Similarly, composite material C is manufactured by Dupont
VTR-5307 was replaced with yet another 3M fluoroelastomer (L-6546, 60% solids).
(containing terpolymer latex). The results of physical tests performed on these composite materials are shown in Table 5 below.

Table: Examples 10A-C Composite materials 10A were prepared using Type 15227 glass cloth (18 oz/yd ² ), which was first thermally cleaned to remove residual size. To this base surface,
A mixture of PTFE (TE-3313) and methylphenyl silicone oil (Dow Corning) was then applied in an amount of 5 oz/yd ² . next,
3M fluoroelastomer (L-6517) and FEP resin [Dupont TE-9503 aqueous dispersion,
A coating layer of a 40/60 ratio blend with 55% solids was applied at an amount of 8 oz/yd ² in several passes. The composite was finished with a top coat of PTFE (TE-3313) in an amount of 5 oz/yd ² to give a composite weight of 36 oz/yd ² . The second composite material 10B is 3ML-6546 fluoroelastomer and Dupont TE-
A third composite 10C was produced using a 40/60 blend with Dupont 9503 instead.
It was manufactured using a 40/60 blend of VTR-5307 and TE-9503. The results of physical tests for these composite materials are shown in Section 6 below.
Shown in the table.

[Table] Examples 11A-C As shown in Table 7, composite materials were manufactured using reinforcing materials other than glass. Composite material 11A, 11
B, 11C according to the method used in Example 2,
A three-component matrix consisting of a PTFE-silicone oil primer, an intermediate blend component, and a PTFE top coat was used.

[Table] The test results of the composite material produced in Example 11 are shown in Table 8 below.

【table】

【table】

【table】

Table: Examples 12A-D Four different composites were made according to the methods of Examples 1 and 2. However, the lubricants/impregnants are (1) FMK-4-10-A [TE-3313 (manufactured by DuPont) containing approximately 93% by weight PTFE and 7% by weight silicone oil and ET-4327 (DuPont); (manufactured by Corning)
(2) ET-4327 methyl in aqueous solution Phenyl silicone (manufactured by Dow Corning)
(3) a mixture of 1 part by volume of ET-4327 methyl-phenyl silicone oil emulsion and 8 parts by volume of tap water); (3) a mixture of 1 part by volume of ET-4327 methyl-phenyl silicone in an aqueous solution; (4 parts by volume tap water); or (4) ET-4327 diluted in tap water (1 part by volume);
8 parts by volume) and 1 part by weight of AQUADAG colloidal graphite dispersion. A second fuse dip of TE-3313 (specific gravity, 1.35) was applied, except that the composite had an initial fuse dip of FMK-4-10-A, followed by the application of lubricant. did. then 4
Seeds were completed according to the methods of Examples 1 and 2. For the resulting material, weight; tensile strength, tear strength and flexural strength and coating adhesion; and MIT flex endurance
was tested. These results are shown in Table 10 below.

【table】

EXAMPLE 13 A composite material using a TE-5489 (low crystallinity, compliant perfluorinated TFE copolymer obtained from DuPont) resin dispersion was prepared as follows. In Example 13, Chemfab (Chemical Fabrics Corp.) Model 116
Thermal cleaning of the glass and the intact TE
-5489 (33% solids, specific gravity 1.23, 9.5 cps) was subjected to four fusion dips. A thermally cleaned substrate of 3.04 oz/yd ² raised the total coverage by about 0.7 oz/yd ² . Microscopic examination of the product showed that the coating encapsulating the yarn and adhering well to the yarn was elastic, crack-free, and blemish-free. EXAMPLE 14 This example shows how heat-cleaned and siliconized 15227 glass cloth (3
This was done by pouring 25 g of TE-5489 onto a 5 inch piece). The moisture was dried in a circulating air oven at 75° C. and the resulting fabric (impregnated with dry polymer) was molded in a 0.040 inch thick Thiase at approximately 400 mm for 10 minutes in a step press. The resulting composite material was extremely flexible and compliant, and the coating was strong, elastic, and scratch resistant. Examples 15A-C Examples 15A and 15B were conducted as follows. After thermal cleaning, two pieces of Chemfab model
129 glass cloth (6.2oz/yd ² ) (ECD225 1/3, 38
x 40) was applied in multiple semifused dip passes through a 50:50 (by weight) blend of TE-5489 and a commercially available perfluoropolymer dispersion (described below), followed by a final dry fusion. It was attached to the arrival pass.
In Example 15A, 7 passes were made through such a blend made with TE-3313 and a 9.54 oz.
A composite material of yd ² was obtained. In Example 15B, 6 passes were made through a blend made with TE-9503 which had been heated and concentrated to 63% solids with experimental material.
A product of 9.52 oz/yd ² was obtained. Regarding these Examples, the following tests were conducted.

【table】

TABLE Example 15C was performed as follows. After thermal cleaning, use Chemifabu model 15227 glass cloth (18oz/
yd ² ) (ECB150 4/3, 8×19) was treated with silicone oil. This is done by mixing the glass cloth with water at a ratio of 1:8.
immersed in ET-4327 diluted by volume, then 650
This was done by drying and baking. A first coat of a 50:50 (by weight) blend of TE-3313 and TE-5489 was then applied by dipping, wiping with a smooth rod, drying and baking at 500°. The weight of this first coat was 5.1 oz/ ^yd2 . Next, apply a top coat of FMK-4-10-B.
It was applied in five consecutive semi-fused passes for a total topcoat of 17.7 oz/yd ² . A 1 oz/yd ² top coat of PTFE was applied in one semi-fused pass with no wiping through 1.30 specific gravity TE-3313. This material is then calendered and finally, 720
It was completed by fusing in one dry fusing pass. The finished composite material was more flexible than those of Examples 1 and 2. The coating is matte and Example 1
Although it feels more compressible than the two coatings, this composite does not rub or
It was durable when subjected to rough handling that caused creases. The warp tensile strength of this composite is 863 lbs/in, and the coating bond strength is
It was 8.9lbs/in. Examples 16A-F Example 16A shows how KEVLAR fabric (approximately 16 x 16 batts, approximately 6.6 OZ/yd ² , yarn texture unknown) was fabricated with undiluted TE-5489.
This was done by subjecting the dispersion to two wiping fusing dips through the dispersion. The temperature in the sintering zone during the two passes was 550°C. The weight of the finished fabric was 8.9 OZ/ ^yd2 . Example 16B was made with the same toughening agent as Example 16A and was subjected to one welding dip through TE-5489 under the same initial operating conditions for Example 16A, with a total weight of 7.90 oz. /yd ² . This was followed by three semi-fused dips through FMK-4-10-B, wiping, and processing in the baking zone at 500㎓, and the total weight was successively
increased to 11.4, 13.5 and 17.0oz/ ^yd2 . The composite was completed with a fusion pass at 700㎓. Example 16C was also made with the same reinforcement as 16A and 16B, but in Example 16C, the initial coating layer was obtained from TE-3313.
It consisted of a blend of 50% by weight of PTFE and 50% by weight of polymer obtained from TE-5489 and was applied as a wipe-off fusion dip at 550°. The total weight of the reinforcement and the first coating layer thus applied is
It was 8.4oz/ ^yd2 . As a topcoat, Example 16B
3 dips of FMK-4-10-B were applied and essentially dry fused as in the case of
A final product of 16.8oz/ ^yd2 was obtained. Three types of products were tested as shown in the table below.

[Table] The reinforcement for Examples 16D, E, and F was made by baking graphite fabric of type No. W-134 (5.8 oz/yd ² approximately 12 x 12 strokes manufactured by Fiberite Corporation) at 680 mm. I then heated it and cleaned it. Example 16D then added the reinforcement to TE-
This was done by passing the 5489 dispersion through two wipe-down fusing dips. Finished weight is
It was 8.3oz/ ^yd2 . To make the material of Example 16E, thermally cleaned graphite is soaked with no-wipe reinforcement through ET-4327 (diluted 1:8 volume with water), then dried and baked at 500°C. In some cases, the material was subjected to silicone treatment. This was then followed by a wipe-off fusing dip through TE-5489 and baking at 550°, resulting in a siliconized fabric of 6.0 oz/yd ² to a total weight of 7.4 oz/yd ² . Three additional wipe-off semi-fused dips of FMK-4-10-B were applied, followed by a bake at 500㎓, the weight after each pass was
They were 11.9, 13.6 and 15.7oz/ ^yd2 . Final printing was performed at 700㎓. Example 16F was made following essentially the same procedure as Example 16E using siliconized reinforcement, but with TE-3313 and TE-5489 instead of TE-5489 as the first coat. A 50:50 solids blend was used. The weight after this process is
It was 7.8oz/ ^yd2 . Thereafter, three wipe-off semi-fusion dips with FMK-4-10-B were applied and dry fused as in Example 16E. The weight of the final product obtained was 15.5oz/ ^yd2 , and the three products were tested as shown in the following table.

【table】

Table: Examples 17A-M Several examples incorporate KALREZ latex obtained from Dupont and identified as 34045-133 by evaporating the dispersion to dryness and forming crumbs. The crumb was then pressed into a film in a corrugated press, and the film was laminated to a substrate, also in the corrugated press, by a lamination process. Example 17A is the model
The 15227 glass was thermally cleaned and siliconized by soaking it through ET-4327 diluted 1:8 volume with water, followed by drying and baking. The treated substrate is then dipped through the Kalrez dispersion, not wiped off, and
The weight of the resulting composite material was 20.8 oz/ ^yd2 . Example 17B is a coated fabric of Example 17A.
This was done by subjecting a portion of the fabric to four semi-fused passes (approximately 150 cps viscosity) through TE-3313 (while wiping with a 40 mil wire wound rod). The resulting 36.2oz/yd ² composite material was approx.
Pressed in a corrugated press at 1300 psi for 1 minute. The surface plate of this press was heated to 325 degrees. The coated surface is covered with a release sheet of Chemfaab 100-10TEGE (PTFE coated glass fiber fabric).
Protected during the pressing process. The composite was then baked at 525°C in a circulating air oven for 20 minutes to remove residual surfactant. The composite, protected with clean aluminum foil on both sides, was returned to the corrugated press and annealed by pressing for 5 minutes at minimum pressure (less than 15 psi) using a heated platen at 720°C. tied. The weight of the resulting composite material was approximately 35.5 oz/ ^yd2 . Example 17C was made by giving a portion of the coated fabric of 17A five wipe passes through undiluted VTR-5307 fluoroelastomer latex. In each pass, it is dried and approx.
Baked at 300-450 〓. The composite was then baked in a 525° circulating air oven for 20 minutes to remove residual surfactant. The final product weight was 32.2oz/ ^yd2 . Example 17D is
A portion of the 17A coated fabric was passed through FMK-4-10-B and subjected to three semi-fusing passes (wiping with a 40 mil wire-wound rod, all passes at 10 in/min.). It was done by doing. The weight at this point is
It was 32.9oz/ ^yd2 . This composite material is then
Bake in a 525〓 circulating air oven for 20 minutes and fuse between sheets of clean aluminum foil for 5 minutes using a 710〓 platen in a step press at less than 15 psi. In 17E, Kalretsu crumb was prepared by evaporating an amount of Kalretsu dispersion to dryness in a circulating air oven at 75-85°C. 10 g of this crumb was placed on one side of aluminum treated with a silicone mold release agent (SPRITS SILICONE MOLD RELEASE, sold by Sprits of Melville, New York). An approximately 18-by-18-inch piece of foil and a silicone resin-coated fiberglass fabric on the other side (from Oak Industries, Inc., Hoosick Falls, New York).
(available as SRC-5) between sheets of the same size. The material was placed between 1/8 inch stainless steel smooth caul plates, pressed on a 550 mm platen with 80 tons of force for 5 minutes, and then cooled under pressure. Circular pieces of Kalretsu film approximately 8 to 10 inches in diameter and varying in thickness from 0.005 to 0.008 inches were obtained. The film was then folded over the edges of the portion of Example 17A such that approximately equal semicircular portions of the film were facing each other on opposite sides of the coating reinforcement of Example 17A. The sandwich was placed in a press between the thickness of the glass cloth, which served as a compression pad, and force was applied to the film to force it into the irregular reinforcement. Aluminum foil treated with a silicone mold release agent was used between the film and the compression pad. A stainless steel caul plate was used. The above laminate was applied on a surface plate with a force of 10 tons (approximately 400-500 lbs/for a 10 inch diameter semicircular composite).
in ² ) at 550° for 5 minutes. The composite material was allowed to cool under pressure. The foil was easily peeled off, yielding a semi-circular laminate composite surrounded by lighter coated reinforcement. This material is put into the press again, 350〓
The sample was placed between sheets of aluminum foil treated with a mold release agent for 5 minutes using 5 tons of force on a surface plate to smooth out any fabric impressions coming through the foil from the compression pad. The finished smooth laminate had a thickness of 0.028-0.029 inches near the center and 0.026-0.027 inches near the edges. Under the microscope,
Even when I examined the front of the fabric or looked at the cut, I could not find any voids. Visually, it was indistinguishable from the dip coated material, except for the complete absence of air bubbles, pinholes and craters. Similar laminated composites were made by the same method as in Example 17E, using the substrates described in Examples 17D, 17C, and 17B. These were named Examples 17G, 17H and 17J, respectively. For ease of comparison, the compositions of Examples 17A-E and G, H and J are summarized in the following table.

【table】

Table: Example 17E was prepared by placing a film made from Karretsu latex as described in the procedure for preparing Example 17E on one side of a piece of Chemfaab type 129 glass fiber fabric that had been heat cleaned.
17K was prepared. This layup is
Protected on both sides by aluminum foil, placed in a corrugated press and using the minimum available force,
Pressed at 550〓 for 1 minute. The material removed from the press was a composite material with a film on only one side that was well adhered to the reinforcement. One single-sided composite material is a contact adhesive [Armstrong's “N-111INDUSTRIAL
bare glass
coated on the surface. The same adhesive was also applied to one side of a swatch of polyester-cotton fabric. After drying, the two adhesive coated materials were pressed together to form a two-layer fabric having one perfluoroelastomer side and one polyester-cotton side. This fabric would be suitable for clothing. Example 17L is a graphite-reinforced perfluoropolymer composite made by using the material of Example 16D as a support and making a laminate according to the method used in making Example 17E. It was done. As previously mentioned, the initial coating on the support was derived from TE-5489, a low crystallinity perfluoropolymer based dispersion. The resulting laminate was approximately 0.015 inches thick, had a smooth resilient matrix, and appeared to be well impregnated with reinforcement. Example 117M uses a 0.005 inch thick PTFE skived film (available from Chemplast Inc., Wayne, New Jersey) to support Example 17D. fabricated by bonding to both sides of a siliconized 15227 reinforcement, which subsequently consisted of an initial coat of Kalretsu, followed by a topcoat of fluoroelastomer-PTFE blend (FMK4-10B). It was a laminated product. This laminate was pressed under the following conditions. In other words, surface plate temperature: 720〓, pressure: about 5
10 tons of force on a specimen approximately 10 inches by 10 inches, time at that temperature.
temperature): 5 minutes, cooled to 500°C under pressure and removed from the press. The thickness of the finished specimen was 0.035-0.037 inch.
The PTFE appeared to adhere strongly to the topcoat. Even after repeated attempts to separate small areas of the laminated topcoat and tear the layers, there was no tendency to pull apart. Examples 19A and B Example 19A was prepared as follows. Chemfaab type 122 glass fiber fabric was thermally cleaned. A first coat of silicone oil lubricant/impregnant and PTFE were then applied simultaneously through a bath of FMK-4-10A in a single dip, followed by drying and baking. The resulting reinforcement is described as a "Fluorel based Diak catalyzed fluoroelastomer compound suitable for flue duct applications."
fluoroelastomer compoand suitable for flue
duct applications”) Passaic Rubber Co., Clifton, New Jersey.
Rubber Corporation, Clifton NJ) was laminated between 0.012 inch sheets of uncured calendered sheet stock identified as Rubber Corporation, Clifton NJ). Brush with acetone on the side of the rubber that will contact the fabric, then lay-up the material and lay-up between 350㎓ plates for 15 minutes at approximately 250-300 lbs/in ² (to specimen). The sandwich was hardened by pressing and cooling to 200°C under pressure. The resulting reinforced rubber had a thickness of about 0.14 inches and was very flexible with good cohesion. Example 19B was made following the same procedure used in the preparation of Example 19A. However, the support used was 15227 as reinforcement and the rubber slabs were not brushed with acetone before stacking. The resulting material also had a thickness of 0.04 inches, appeared to have equal flexibility when compared to Example 19A, and also had good cohesion. Example 20A and B Triallylisocyanurate (TAIC) [Nippon Kasei Chemical Co., Ltd.
Company, Ltd., manufactured by Mitsubishi International Corporation, New York, New York.
Available in the United States from )
Kalretsuklam, which contains 1.5 parts of per 100 parts of rubber, is added to
% solution to the Kalrez dispersion and by evaporating the treated latex to dryness at about 90°C. Addition of TAIC in this manner did not appear to cause clotting. Two composite materials were made following the same method used in preparing Examples 17E, G, H and J. One was performed on Example 17A, designated Example 20A, and one was performed on Example 16A, designated Example 20B. Each of these composites was irradiated with 1 MeV electron beams to a total dose of 4, 8, and 16 megarads, respectively. The beam current used was 5 milliamps. Dynamic modulus measurements on irradiated composites indicate that crosslinking was induced by the radiation. Example 21 Composite materials produced according to the method of Example 2 were stacked and laminated in a corrugated press. A 0.005 inch FEP film was used as the hot melt adhesive between the layers and the following lamination conditions were used. Surface plate temperature: 670〓 Pressure: about 500 psi Time at temperature: 6 minutes 2 differs in the relative arrangement of the warp threads within the layers
Four examples of layer laminates were manufactured. These had warp threads parallel (0° skew), 30° skew, 45° skew and perpendicular (90° skew). The composite material made according to Example 2A also
Press conditions similar to those above, but at a lower pressure of approximately 280 psi (45 psi for 18" x 18" laminate)
laminated using tons of force). 0, 30, 45 and 90 degree ply warp arrangements were also used in the manufacture of these examples. The laminates were tested for strip tensile strength and trapezoidal tear strength. The results of these tests are reported in Table 16 below.

[Table] Example 22 Glass fiber knit fabric of approximately 5oz/yd ² weight,
Non-wipe soaking was carried out through Dow Corning ET-4327 which had been diluted 1:8 volume with tap water, dried and baked. The treated knit support is then subjected to a single dip through a Kalrez dispersion, dried and
Baked at 700㎓. The coated reinforcing agent,
Sandwiches placed between layers of film prepared from Kalrez and protected with aluminum foil treated with silicone mold release agent were heated at approximately 100 psi for 5 minutes.
It was pressed between 550 mm surface plates and cooled under pressure.
The resulting composite material was soft and flexible. Example 23 Method used in preparing Example 22 (with the exception of
Different lamination conditions, i.e. platen temperature of 720〓,
FMK reinforced with glass fiber knit fabric that had been primed with ET-4327 and dip coated in Kalletz latex (approximately 500 psi pressure, 3 minutes at said temperature, then cooled under pressure)
A laminate was made using the -4-10-B film. Examples 24A-D PFA, FEP and PTFE as top coats
and as a resin component in top coats of perfluoropolymer/fluoroelastomer blends.
A series of four specimens similar to Example 2A were prepared, comparing PFA and PTFE. The composition of the composite material is summarized in the table below.

Table: All composites were pressurized in a similar manner to Example 2A. The first layer was applied with a non-wipe fusion dip. The top coat was applied in multiple wipe-off semi-fused dips to give a total fabric weight of approximately 40 oz/yd ² . The fabric was calendered to harden the semi-fusible layer, dry fused and completed using a single non-wipe fusing dip through the topcoat dispersion. A sample of the material was tested for initial physical properties, and the results are shown below.

【table】

Table: Examples 25A-3C A piece of 0.003 inch thick copper foil etched on one side (Yates Industries, Bordentown, New Jersey).
Industries, Inc., Bordentown, New Jersey)
(available as type "A" etch) from Phys., Inc.) was washed with soap and water, rinsed with distilled water, washed with reagent grade acetone, and air dried. 1% of this etched surface
γ-Aminopropyltriethoxysilane [Union Carbite Corporation, New York, New York]
available as A-1100 from New York). ] Immersed in an aqueous solution and then in an air circulation oven
Processed by drying at 225°C. Laminates were made on the treated foil support as shown in the following table.

[Table] Processed.
TE-9489, as supplied by DuPont, contains a high temperature methyl-phenyl silicone oil. Example
When this dispersion is dried to form a crumb and the crumb is pressed into a film according to the method of 17E, the silicone oil is impregnated into the film and applied to the hot pressed laminate. Prevents adhesion of other ingredients. To remove this silicone oil, the cast film is shredded.
Ross Mixer emulsifier (Ross Mixer−
The film was washed with clear toluene in an emulsifier, dried in a circulating air oven at 50°C and repressed into a film. This was repeated four times to obtain a silicone-free film. This film was used in making Example 25B. Three examples are foils with durable, compressible polymer coatings. Example 25B bonded very firmly to the copper surface. It had a particularly soft but elastic coating. The coating can be carved with a knife but does not show any tendency to delaminate even in boiling water. Example 25C has a somewhat less elastic and less flexible coating than 25B, but the resistance to delamination appears to be the same. Example 25A had similar coating properties to 25C, but was the easiest to carve of the three. Example 26 A piece of cold rolled steel, typically 16 gauge, was sanded on one side with 200 grit sandpaper until the surface was shiny, shiny and free of mill scale and rust. The surface was washed with reagent grade acetone, air dried, submerged with 6N sodium hydroxide solution, allowed to stand for several minutes, washed with distilled water, and air dried. This surface is treated with silane,
A polymer film composed of a resin derived from TE-5489 was press laminated to the surface (following the method of Example 25B). soft, compressible,
A sheet steel with an elastic coating was obtained, which was firmly bonded and did not show any tendency to delamination when carved with a knife. Example 27 A piece of 1/8 inch window glass was cleaned with soap and water, rinsed with reagent grade acetone, immersed for several minutes in 6N sodium hydroxide solution, rinsed with distilled water, and washed with distilled water.
I let it air dry. This surface was treated with silane, and a silicone-free TE-5489 film was press laminated to form a glass support. This is essentially an example
25B and 26 were followed, but for specimens
Using very low pressure, less than 50 psi, and starting at room temperature with the platen, allow the platen to heat up to 550 psi over a period of approximately 1/2 hour, and air cool to room temperature over a period of several hours. This was done by avoiding thermal shock that might destroy the glass. TE-5489 is an elastic material that did not delaminate after 24 hours of exposure in boiling water.
Resulted in a 0.005 inch coating. Example 28 A thin extruded coating of PTFE was applied to ECG37 1/3 glass fiber yarn by paste extrusion.
The sheathed yarn thus produced is woven into approximately 14
It was made into a plain weave fabric with 15 stitches. The weight of this fabric is approx.
35oz/ ^yd2 , approximately 60% of which is PTFE.
The topcoat layer was applied as follows. FMK-4
-10-B cast film in a stage press,
Laminated on both sides of the support at a pressure of about 280 psi.
A platen temperature of 700° was maintained for 5 hours and then cooled under pressure to about 150° over a period of about 15 minutes. The resulting product weighs 41oz/
yd ² , had excellent physical integrity and was exceptionally flexible. Example 28B TE-3313 and fluoroelastomer (L-9025
latex (obtained from 3M)
A cast film of a 60/40 weight percent blend of was laminated to the support of Example 28A. The resulting product had flexibility and integrity comparable to Example 28A. Example 28C The support fabric of Example 28A was used as FMK-4-10-B.
It was subjected to eight semi-fusing passes through and then a final dry fusing pass. This gives a thickness of 0.044
A material weighing 52.4 oz/yd ² was obtained.
Although the product was 20% heavier and approximately 30% thicker than Example 2A, it had excellent integrity and
It was somewhat more flexible than 2A. When this product was subjected to physical testing, the following results were obtained. Trapezoidal tear strength (warp direction) 260 lbs. Elongation at 40 lbs/im load (warp direction) 4.5% Example 29 A type 15227 glass fabric support was heat washed and
Impregnated with ET4327 methylphenyl silicone emulsion. The first layer of perfluoroelastomer was applied in a single fusion dip operation through DuPont TE-5506 (a perfluorinated polymer in aqueous dispersion with a specific gravity of 1.39 and low experimental crystallinity). 104 parts by weight of TE-3313 (PTFE solids, 57.7%)
and 154 parts by weight of Karretsu latex (perfluoroelastomer solids, 26%). The mixture was evaporated to dryness in a circulating air oven operating at 90°C. Shred the resulting cake and put it in a Waring blender
Washed several times in hot water and dried again at 90°C to obtain a coarse, flaky crumb. Example
Using the technique used in making 17E, the crumb was pressed into a film and the film was laminated to a support. Support weight is 24.7oz/
It was yd ² . Both the film and the laminate were pressed under the following conditions. Namely, surface plate temperature: 550〓, force on surface plate: 20 tons (approximately 560 psi for film, 1100 psi for laminate), time at above temperature:
It was hot in 3 minutes. The resulting flexible product had a thickness of approximately 0.040 inches, exhibited good physical integrity, and had a resilient, well-adhesive, tough coating. Example 30 A film was prepared from a TE5489 derived solid treated to remove silicone oil as described in Example 17E. 10 g of toluene-washed crumbs were pressed between pieces of aluminum foil treated with a silicone mold release agent in a corrugated press. The surface plate was operated at 325〓 with a force of 1 ton for 1 minute.
Thereafter, the material was cooled under pressure. The resulting film was made into a piece of 100% polyester knit fabric, model 5126, white, 1980 [Armtex, Inc., Pilot Mountain, North Carolina].
Carolina). ] and pressed essentially as described in Example 17K.
However, the surface plate temperature is 325〓, the force on the surface plate is 10 tons,
The condition was 1 minute. A durable flexible composite material having a thickness of approximately 0.015 inches was obtained. The knit reinforcement was well encapsulated by the perfluoroelastomer matrix. Example 31 Using the method described in Example 30, TE5489
5g of solid is pressed into a film and one sheet of
TYVEK polyolefin non-woven fabric (spunbonded
Polyolefin), model 1056D (manufactured by DuPont), was laminated on one side. The material was laminated using a platen temperature of 240°. That is, on the surface plate, about 1
It was pressed for 2 minutes with a force of tons. After holding the temperature and pressure for 1 minute, the material was cooled to about room temperature under pressure. The resulting laminate contained perfluoropolymer (approximately 0.009 inch thick) on one side and was flexible and strong. Examples 32A and B Using a method similar to that described in Example 31, TE-5489 fluoroelastomer was injected into two types of REEMAY polyester nonwoven fabrics (spun-
A laminate was produced by laminating it on bonded polyester (manufactured by Dupont). Example 32A is Dupont model
Contains 2431 reinforcement, Example 32B is Dupont type
Contained 2024 reinforcement. In the two examples, the pressing conditions were as follows. That is,
The conditions were as follows: temperature of the surface plate: 335〓, force on the surface plate: 2 tons, time at the temperature: 2 minutes, and pressure cooling. The composite thus produced contained perfluoropolymer on one side and polymer on the other side. Furthermore, the composite material was flexible and strong. Example 33 Example 33 was conducted using the materials and methods used in Example 30. However, the lamination pressure was reduced to yield a composite having perfluoropolymer on one side of Armtex Model No. 5162 polyester knit. The pressing conditions were: platen temperature: 335°, platen force: 1 to 2 tons, time at this temperature: 1 minute, and pressurized cooling. The resulting laminated composite material was 0.012 inches thick and was significantly more flexible and consistent than that of Example 30. The polymer matrix bonded tightly to the reinforcement and did not exhibit any tendency to delamination. EXAMPLE 34 Using the method of Example 33, a single-sided laminate using a resin derived from TE-5489 was fabricated on a 50/50 polyester/cotton double-sided fabric (1.85 yield at 60 inch width) in New York. Burlington Industries, New York
Model No. 443833] manufactured by A.A. Industries, New York, New York). The resulting product was a durable, flexible, consistent laminate. Perfluoropolymer was firmly fixed on one side. The non-laminated side of the composite maintained its soft woven quality. Examples 35A and B Examples 35A and B were carried out using essentially the same methods as used in Examples 2A and 2B.
However, instead of DuPont VTR/5307 latex in the PTFE/fluoroelastomer latex blend, AFLAS TFE/propylene copolymer latex (obtained from Xenox, Inc., Houston, Texas) was used. ] was used. Dupont TE−3313 104
parts by weight and 129 parts by weight of AFLAS latex to determine the ratio of PTFE to fluoroelastomer.
I kept it at 60/40 and created a blend. Example
The compositions of 35A and B are shown below.

【table】

【table】

[Table] Examples 36A-C Example 36A was carried out using the following procedure. ECB150 4/3 Glass fiber thread treated with silicone oil to create TE-5506 and TE-4327 emulsion [manufactured by Dow Corning]
TE-5506 low crystallinity perfluoropolymer (Dupont) in a single application using a mixture of
The material was impregnated with the following materials (manufactured by J.D. Co., Ltd.), then dried and fused. 199 parts by weight of TE-5506 (50.3% solids)
A bath was prepared by mixing with 23 parts by weight of ET-4327 (35% solids) and diluted with water to a specific gravity of 1.225.
The ratio of perfluoropolymer to silicone polymer in this bath was 12.5 to 1 by weight. The impregnated yarn prepared according to Example 36A was woven into a 14×14 batt fabric having a weight of approximately 20 oz/yd ² . The fabric was then baked at about 550°C for 1 minute and used to prepare Example 36B as follows.
and 36C. Example 36B is Example 36A
fabric with an intermediate coating of PTFE/fluoroelastomer blend (weighing approximately 13 oz/yd ² ).
This was done by applying four semi-fused baths through FMK4-10-B. The coating is fused by baking at approximately 700°C for 1 minute, and the PTFE
The topcoat was diluted to a specific gravity of 1.30.
3313 (manufactured by DuPont). The final product weight for this example was 34oz/ ^yd2 . Example 36C applies an intermediate coating of PTFE to the fabric of Example 36A in six semi-fused dip passes through TE-3313 with a specific gravity of 1.485, then calendered, dry fused, and with a specific gravity of 1.30. TE−
This was done by doing a final fusion dip through 3313. No top coat was applied. When the products of Examples 36B-C were subjected to physical tests, the following results were obtained.

[Table] Although typical uses and embodiments of the present invention have been described above, those skilled in the art will be able to make many variations and modifications of such embodiments without departing from the technical idea of the present invention. By the way,
Additionally, it is intended to claim all such variations and modifications that fall within the scope of the invention.

[Brief explanation of drawings]

1 and 1A depict enlarged schematic cross-sectional views of a woven composite material thereby illustrating and explaining several embodiments of the present invention, and FIG. 2 depicts an enlarged schematic cross-sectional view of one embodiment of the present invention. FIG. 3 is an enlarged schematic plan view of a cross-section of an open-weave glass fiber composite coated according to an embodiment; FIG. FIG. 4 is a diagram showing the relationship between rate and exposure time, and FIG.
The composite material of the present invention of Example 2 was heated to 2N at the boiling point.
It is a diagram showing the relationship between tensile strength retention and exposure time when immersed in sulfuric acid Explanation of drawing numbers, 10... Yarn, 12... Fluoropolymer initial coating layer, 14... Warp, 16 ... Weft, 18 ... Top coat layer, 20 ... Top coat,
22...Lightweight layer of lubricant and fluoropolymer,
24...Opening, 26...Top coat layer.

Claims (1)

[Scope of Claims] 1. A composite material comprising a substrate coated with a matrix and susceptible to the corrosive action of hydrogen fluoride, the matrix comprising: (A) a perfluoroplastic or a perfluoroelastomer or a combination of a perfluoroplastic and a perfluoroelastomer; (B) a perfluoropolymer selected from the group consisting of a blend or any combination thereof; and (B) a fluoroelastomer or a fluoroplastic or a fluoroelastomer/fluoroplastic blend or any combination thereof; A composite material having a topcoat layer that is distinct in its composition, provided that the topcoat layer includes a hydrogen-containing fluoropolymer if the initial layer is a perfluoroplast. 2. The composite material of claim 1, wherein the initial layer comprises a perfluoropolymer and a lubricant. 3. The composite material of claim 1, wherein the substrate is treated with a coupling agent to promote bonding. 4. The composite material of claim 1, wherein the overcoat layer comprises a blend of a fluoroelastomer and a fluoroplast, and the fluoroelastomer comprises from about 10 to about 90% by weight of the blend. 5. The composite material of claim 4, wherein the fluoroelastomer constitutes 25-60% by weight of the blend. 6 Claim 4, in which an intermediate layer containing a fluoroelastomer is interposed between the first layer and the top coat layer.
Composite materials as described in Section. 7. A composite material according to claim 1 having a top coat selected from the group consisting of a fluoroplast or a fluoroelastomer or a fluoroplast/fluoroelastomer blend or combinations thereof. 8. A composite material according to claim 1, wherein the resin in the layer is at least partially crosslinked. 9. Composite material according to claim 1, wherein only one side of the substrate is coated with a matrix. 10. The composite material of claim 1, wherein the substrate is a reinforcing agent that can withstand the composite manufacturing temperatures. 11. Composite material according to claim 10, wherein the substrate is a thread or filament or monofilament or other fibrous material. 12. Claim 10, wherein the substrate is a woven fabric selected from the group consisting of fibrous materials and non-woven materials.
Composite materials as described in Section. 13 The base is glass, glass fiber, ceramic,
Graphite (carbon), polybenzimidazole, polyalamide, polytetrafluoroethylene metal, polyolefin, polyester, polyamide, copolymer of tetrafluoroethylene, polyether sulfone, polyimide, polyether ketone, polyethenimide, novoloid phenolic fiber, natural textile material 13. A composite material according to claim 1 or claim 12, selected from the group consisting of synthetic textile materials. 14. Composite material according to claim 1 or 7, wherein the fluoroplastic consists of PTFE, PFA or FEP. 15. A patent in which the fluoroelastomer is selected from the group consisting of copolymers of vinylidene chloride and at least one other fluorinated monomer selected from the group consisting of hexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, pentafluoropropylene. Claim 1
Composite material according to item 7 or item 7. 16. Composite material according to claim 1, wherein the fluoroplastic consists of PTFE, PFA or FEP. 17. The composite material of claim 1, wherein the perfluoroelastomer comprises a copolymer of perfluorovinyl ether, such as perfluoromethyl vinyl ether (PMVE) or perfluoropropyl vinyl ether (PPVE), and tetrafluoroethylene (TFE). 18. The composite material of claim 1, wherein the fluoropolymer component can contain functional groups selected from the group consisting of carboxyl, sulfonic acid and its salts, halogen, and reactive hydrogen on an alkyl side chain. 19. A method for producing a composite material comprising a substrate susceptible to the corrosive action of hydrogen fluoride coated with a matrix, the matrix () substantially shielding the substrate from chemical attack without loss of flexibility. first applying an initial layer comprising a perfluoropolymer selected from the group consisting of perfluoroplastics or perfluoroelastomers or blends of perfluoroplastics and perfluoroelastomers or any combination thereof in an amount sufficient to , a fluoroelastomer or a fluoroplastic or a fluoroelastomer/fluoroplastic blend, or a combination thereof, and where the initial layer is a perfluoroplastic, applying a topcoat layer comprising a hydrogen-containing fluoropolymer to the initial layer; A method of manufacturing the composite material formed by stepwise application of a fluoropolymer layer comprising: 20. The method of claim 19, wherein the initial layer comprises a perfluoroelastomer, a lubricant, and a coupling agent. 21. The method of claim 19, further comprising application as a top coat form.