JPH0479982B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION This invention relates to bundles of chemically treated fibers such as strands or yarns for use in woven fabrics, with particular application when coated or laminated to polymeric films. [Prior Art] Chemically coated textiles are manufactured by coating or laminating polymeric films onto textiles and are used in a wide variety of products. Initially, coated fabrics consisted of cotton fibers coated with wax, oil, or natural rubber to make the material waterproof. With the advent of synthetic polymers, polymeric films used in textiles include polyvinyl chloride, polyurethane, silicone polymers, polytetrafluoroethylene, polyethylene, chlorosulfonated polyethylene, and chlorinated polyethylene polymers made from ethylene, propylene, and diene monomers. rubber, neoprene, and synthetic rubbers such as Hypalon rubber and nitrile rubber. With the development of various polymer film materials, advances have also been made in textile materials including textiles. For example, polyesters, polyamides like nylon, Kevlar
Fibers such as aramid fibers, rayon, graphite, glass fibers and other organic or inorganic man-made fibers can be mentioned. Coated textiles have a wide range of applications, from architectural and construction applications to industrial and commercial textile applications to the geotextile sector. Construction applications include air and tension structures such as stadium tension and/or air supported canopies.
tension structure). There will also be 425,000 ^m2 of clad fabric roofs for airport facilities and 26,000 ^m2 of air-supported clad fabric roofs for stadiums. On the other hand, examples of industrial and commercial applications include canopies, linings, awnings or tarpaulins for water storage, swimming pools, ponds and garbage dumps. Applications in the geotextile field include civil engineering applications such as road repair systems. In these various applications, many applications have common performance requirements for the covering fabric, but some applications may require special performance. These required performances include contributions from the uncoated fabric and the covering polymer film, and contributions from their combined contributions. Performance requirements from textiles include tensile strength, flexibility, weather resistance, chemical resistance, tear strength, resistance to tear propagation, and dimensional stability to minimize elongation under load. properties, stability under various temperatures and humidity, abrasion resistance, and adhesion to polymeric films. Other useful properties of coated fabrics include fire protection, particularly for architectural and construction applications. [Problems to be Solved by the Invention] Some fiber materials used in polymer-coated textiles lack one or more of the above-mentioned required performances. For example, inorganic fibers such as glass fibers have good dimensional stability, are nonflammable, and have excellent rigidity, but they also have the necessary flexibility, abrasion resistance, and polymeric film coating or lamination on textiles. Lacks stickiness. Additionally, when fiberglass is used in the fabric to be covered, traditionally greige
goods) are used. The production of glass fibers typically involves applying an aqueous chemical treatment composition to the thin filaments that flow out of the bushing of the furnace in which the glass was melted as a stream of molten glass.
treatment composition). The filaments are combined into strands, and the strands are twisted or untwisted into yarn. Gray zigs are obtained by weaving fiberglass yarns. The yarn is then thermally cleaned to remove the chemistry of the sizing composition. Heat cleaning of the glass fiber yarns reduces the inherent strength of the glass fibers in some respects, thus attenuating the strength properties of the glass fiber cloth. The shortage of glass fibers may not be alleviated by forming composite strands containing various types of organic fiber materials in the glass fibers. By using fibrous materials and polymeric films in this way, coated fabrics are typically produced with a thickness of the order of 1 mm and a total weight of more than about 750 grams ^per square meter. The polymeric film in the coated fabric provides airtight color and abrasion resistance to the original fabric. Even if organic fiber materials are used for the fabric, the chemical bond between the coating and the fabric is not very strong, despite the presence of adhesion promoters to the fabric in the polymeric composition that makes up the film. isn't it. It is an object of the present invention to provide a flexible and abrasion resistant textile material, resulting in an improvement in coated or laminated textile products. It is further an object of the present invention to provide a textile material with improved flexibility and abrasion resistance, which can be manufactured into coated textile products without requiring heat treatment of the textile material or fabric. The goal is to bring improvements to fabrics that have never been woven. SUMMARY OF THE INVENTION The object of the present invention set forth above and other objects of the present invention which will become apparent from the following description is to provide a method for treating dry residues of partially cured aqueous chemical treatment compositions. This is achieved by a bundle of coated, impregnated and sized monofilaments. Aqueous chemical treatment compositions include water-soluble, dispersible, or emulsifiable elastomeric ethylene-containing interpolymers, such as copolymers or terpolymers made from ethylene monomer and one or more polar comonomers; It is made of a crosslinkable polymeric material that is flexible, dispersible, or emulsifiable. Ethylene-containing interpolymers are
It has a low glass transition temperature of about 0°C at most. and one or more polar comonomers that result in an essentially amorphous copolymer or terpolymer with sufficient ethylene segments to achieve this desired glass transition temperature. Interpolymers contain the solids content of aqueous chemical treatment compositions as a major component. Water is present in the composition in a predominant amount such that the total solids content and viscosity are effective to impregnate the filament bundle. In this impregnation, the partially cured dry residue of the aqueous impregnation composition is
The crosslinkable material is impregnated to such an extent that most of the filaments are separated to some extent from each other over a substantial portion of the bundle of filaments that are coated and impregnated. A dehydrated and dried residue of the coating to provide a non-tacky outer surface is present in the aqueous chemical treatment composition in an amount effective to effect partial curing. The aqueous chemical coating compositions can optionally include water-soluble, water-emulsifiable or water-dispersible waxes, plasticizers, diene-containing elastomers and crosslinking control agents. The diene-containing elastomer latex is usually present as an optional component, except when the polar comonomer for the ethylene-containing interpolymer forms a eutectic with the polyethylene crystal structure. In this case, the diene-containing elastomer must be present as at least a minor part of the solids content of the coating composition. The diene-containing elastomer is essentially free of vinylpyridine. The aqueous chemical treatment composition impregnates the bundle of filaments, but the filaments have dried residues of the aqueous sizing composition. During the process of forming filaments, the aqueous sizing composition is used to protect the filaments from inter-fiber damage and, if necessary, to make the surfaces of the filaments more compatible with the hydrophobic coating layer. decrease. The impregnated monofilament bundles are sufficiently flexible to be woven into fabrics by themselves or with other monofilament bundles. Fabrics can be coated by impregnation and saturation filling, surface coating with solvent-containing coatings or plastisols, and lamination with films or sheets of coating polymeric materials. It will be done. Effects and Examples Bundles of monofilaments, strands, rovings and bundles of twisted and untwisted strands and yarns having sufficient flexibility to be woven are according to the invention: It can be manufactured without the need to heat clean the bundles to remove chemical treatments. Normally, when glass fibers are manufactured as continuous single fibers by conventional methods, the single fibers are
Treated with a sizing composition whose chemical composition protects the filaments from rubbing and rubbing, which occurs when the filaments are processed during processes that involve various contacts and guide eyes. be done. When weaving a fabric or cloth from continuous fibers or collections of fibers such as strands or collections of strands or yarns, the longitudinal yarns or warp threads of the woven fabric undergo considerable wear from the moving parts of the loom. Easy to accept. Wear against the warp threads is caused by the split rod of the loom.
guide surfaces, drop wires, confuser bars, heddles, reeds, shuttles and adjacent yarns. To protect the warp yarns from such abrasion, slashing chemical compositions are commonly used. Once the fabric is woven, the woven fabric has warp yarns that have a sizing composition and a slushing sizing composition that are present on the filaments from the time of their formation, while the weft yarns within the fabric have a It only has a signing composition. Additional coating of the warp yarns with a slushing sizing composition causes the warp and fill yarns to have different surface properties within the same woven fabric. These differences can be detrimental to the drying of the fabric, the handling and feel of the fabric, or the electrical and reinforcing properties of the fabric when used with polymeric coatings. Therefore, the fabric is typically heat cleaned to remove both the forming sizing composition and the slushing sizing composition to incorporate the yarns into the fabric. For example, for glass fiber strand yarn cloth, heat treatment is approximately 482-705℃
(900-1300〓) for about 10-180 seconds or longer to volatilize the solids and remove them from the fabric, softening the glass fibers in the fabric and placing them in their new positions.
Although glass fiber strands typically have tensile strength, dimensional stability, and resistance to chemical, photochemical, and microbiological degradation, the heat treatment process attenuates some strength properties of the glass fiber strands. Monofilaments such as polyester, nylon and polyamides such as Kevlar result in fabrics that are coated and laminated with polymeric films.
Glass fiber strand yarns have the same flex fatigue resistance as polyester and polyamide yarns.
fatigue property) and low density. More flexible filament bundles can be impregnated filament bundles of the invention, in particular glass filaments, strands, yarns, and even polyesters and polyamides. The impregnated monofilament bundle is
Fracture strength characteristics and flex fatigue resistance
It maintains these properties even when exposed to high humidity or water for long periods of time, and has good adhesion to polymeric film coating matrices. The sized monofilament bundles of the present invention have an impregnant that is the dried residue of a partially cured aqueous impregnating composition. The aqueous coating has a predominant amount of solids consisting of an elastomeric ethylene-containing interpolymer. Interpolymers, usually copolymers or terpolymers, are formed from ethylene monomer and one or more polar comonomers. The comonomers can vary from eutectic with the polyethylene crystal structure to substantially amorphous interpolymers. Non-exclusive examples of these comonomers are vinyl acetate, methyl acrylate, ethyl acrylate, styrene, alpha-methylstyrene, methyl methacrylate, acrylamide, methacrylic acid,
n-methyl-N-vinylacetamide, diethyl fumarate, diethyl maleate, vinylpyrrolidone, n-vinylsuccinimide, and mixtures thereof. The interpolymer has a sufficient ratio of ethylene to polar comonomer to have a glass transition temperature (Tg) of about 0°C or less. The glass transition temperature is determined by any method known in the art, such as the ratio of nuclear magnetic resonance peak values, or approximately, by simpler techniques such as differential thermal analysis. Although homogeneous interpolymers are preferred over heterogeneous or alternating copolymers or terpolymers, types of heterogeneous or alternating copolymers or terpolymers may also be used up to certain limits. can. A homogeneous interpolymer is formed from two or more monomers of equal reactivity polymerized at any conversion, or if the monomers have different reactivities, the conversion is determined by interpolymerization. It is produced at low conversion rates during which the comonomer concentration remains almost constant. Heterogeneous and alternating copolymers are known to those skilled in the art. The interpolymers can also be water-soluble, water-emulsifiable or water-dispersible by means of suitable emulsifiers and/or solvents. The interpolymers can be prepared by conventional methods in the ethylene copolymer art. A particularly useful elastomeric ethylene-containing interpolymer is an ethylene vinyl acetate copolymer containing about 25 mole percent or more, or about 45 to 80 weight percent, vinyl acetate monomer in the copolymer. The copolymer is also a copolymer of ethylene vinyl acetate.
Contains sufficient ethylene comonomer such that the Tg is 0°C or less. A non-exclusive example of ethylene vinyl acetate copolymer is air-vinyl acetate copolymer.
Air Products and chemicals, Inc.
airflex 410 vinyl acetate/ethylene copolymer. The copolymer has the composition A _x -B _y , where A is C ₄ H ₆ O ₂
, B represents C ₂ H ₄ . The appearance of the emulsion is a white mobile liquid with a Brookfield viscometer model LVE (25
℃, 60 rpm spindle No. 2 or No. 3), the SUS viscosity at 37.8℃ (100〓) was 100
~2000. Also, emulsion has a pH of 4 to 7.
The content of volatile components is 45-53% by volume, the specific gravity is 1.1, and the density is 9 pounds per gallon. The aqueous dispersion has very small polymer particles in water and contains formaldehyde up to 0.1% by weight,
No other photochemically reactive or reactive chemical solvents are added. The amount of residual unpolymerized monomer is less than 0.5% of the total amount. The amount of ethylene-containing interpolymer in the aqueous impregnating composition is sufficient to impregnate the filament bundle and form a nearly continuous film over a substantial portion of the surface of the filaments in the filament bundle. This is an effective amount. Also, the amount is
It is also an effective amount to form a film on a bundle of single fibers. Generally, that amount will be the predominant amount of solids in the aqueous impregnating composition. In addition to the ethylene-containing interpolymer, the aqueous chemical impregnation composition includes one or more crosslinking materials. Suitable crosslinking materials are compounds that are at least self-crosslinkable at ambient or elevated temperatures and atmospheric or sub-atmospheric or super-atmospheric pressures;
monomers, oligomers and resinous polymers. Self-crosslinking means that the material does not need to be crosslinked with the ethylene-containing interpolymer. Polymeric crosslinking materials are crosslinked by internal crosslinking or external compounds. external cross-linking
Crosslinking refers to the crosslinking of polymers with special resinous polymeric crosslinking materials known in the art. Examples of resinous polymers include polymers such as epoxy polymers, methylol condensation polymers, polyurethanes, and polyesters, polybutadiene, polyisobutylene,
Examples include polymers that are not rubbery polymers, such as styrene-butadiene-vinylpyridine terpolymers and styrene-butadiene copolymers. Non-exclusive examples of crosslinked materials are melamine formaldehyde and hexakis/
Condensates, monomers, dimers, trimers and higher oligomers containing methylol. Furthermore, as phenols or resorcinols, cresol and mixtures of its isomers, xylenol or mixtures of its isomers, mixtures of phenol homologs and compounds of dihydric phenols such as phloroglucinol, resorcinol, cresorcinol, metaxylorcinol. can be given. The aldehyde is
Includes any methylene donor used in place of formaldehyde. Examples include paraformaldehyde, hexamethylenetetramine, acid aldehyde, furfural and mixtures thereof. Aldehydes or methylol condensates are used with acid or base catalysts. Internal hardening can also occur by removing stabilizing components. For example, polyvalent metal ions can be used as volatile complexing agents.
It is stabilized by the addition of complexing agents). Once the impregnating agents are applied, their components evaporate, binding the metal to two or more sites of the polymer in the crosslinked coating. For example, zinc or zirconium salts can be used to stabilize by adding excess ammonia. When the impregnation agent is applied, the ammonia evaporates, leaving a flexible crosslinked impregnation agent. This principle is also used to deactivate catalysts. For example, toluenesulfonic acid, which is used as a catalyst to cure urea resins, is deactivated by volatile amines. When an impregnating agent is used, the amine-acid complex is decomposed by evaporation of the amine and the coating is cured. crosslinking is easy;
Since it is also compatible with ethylene-containing interpolymers, it is preferable to include one or more melamine formaldehyde resins. A particularly preferred melamine formaldehyde resin is an aqueous melamine formaldehyde resin with less than 2% free formaldehyde, less than 5% methanol and
Monsanto's Resimene 841, which has a boiling point of 99°C (210°C). Regimen 841 has a methanol vapor pressure of 95 mm.
Hg, the vapor pressure of water is 17.5 mmHg, the vapor density of methanol is 1.11, and the vapor density of water is 0.64.
1.25, the content of volatile components is 29% by volume. The amount of crosslinking material in the aqueous impregnating composition is an amount effective to reduce the moisture content of the aqueous impregnating composition and cause at least partial curing of the dried residue. This partial curing controls the dehydrated surface tack of the impregnant residue and allows the impregnated monofilament bundle to be rolled out substantially uniformly from its wound package. Partial hardening due to crosslinking can be reduced if the filament bundle consists of larger diameter filaments.
When the filament bundle consists of filaments of finer diameter, the partial hardening can be increased more than in the case of filaments of larger diameter. When the impregnated bundle is densely packed by a wound package cage,
The bundle becomes sensitive to tack and partial curing with a greater degree of crosslinking is preferred. Due to the controlled surface viscosity, the bundle of single fibers impregnated with the aqueous impregnating composition, water reduced, and dried can be incorporated into the loom process without using the loom feeder. . Even if a feeder is used in the loom, surface tackiness cannot be precisely controlled and may partially reduce hardening. Partial curing reduces the water content of the aqueous impregnating composition to achieve a hardness or modulus of the dried residue such that the flexibility of the impregnated monofilament bundle is improved by at least a factor of two. is preferred. This improved flexibility exceeds that of a similarly made unimpregnated bundle of single fibers. In addition, partial curing causes further curing of the dry residue of the aqueous impregnating composition that is impregnated into the filament bundle. This further hardening primarily results in external adhesion of the filament bundle and the polymeric film coating that is ultimately used on the fabric of the impregnated filament bundle. It also creates some additional internal adhesion, furthering the integrity of the filament bundle achieved through partial curing. The limit on the extent of partial curing by crosslinking is such that the flexibility of the impregnated filament bundle is not lower than that of the unimpregnated bundle. In addition to the crosslinking material, the aqueous impregnating composition includes a crosslinking modifier that adjusts the degree of crosslinking between the self-crosslinking material and possibly the self-crosslinking material and the ethylene-containing interpolymer. This crosslinking regulator is
Things like ammonium hydroxide to change the PH of the coating composition, or acid catalysts for crosslinked materials. A non-exclusive example of the latter is the American
40% of American Cyanamide
There is an isopropanol solution of toluenesulfonic acid commercially available as Cycat 4040, which consists of 100% acid and 60% alcohol. Additionally, in the absence of a crosslinking modifier, one of the monomer units in the ethylene-containing interpolymer provides a less tacky film and increases the softening point of the interpolymer, depending on its concentration in the interpolymer. The crosslinking modifier also helps control the hardness or modulus of the coated film. The amount of crosslinking modifier used in the aqueous impregnating composition will vary depending on the strength of the modifier, but
The amount is evaluated in relation to the amount of crosslinking material that achieves partial hardening of the residue of the aqueous impregnating composition. Water in aqueous chemical treatment compositions is the predominant amount in the composition, including volatile and non-volatile portions. The amount of water is such that the total solids concentration and viscosity of the composition provide a composition that is capable of impregnating bundles of filaments, including bundles of strands and yarns. The degree of impregnation of the bundle of filaments is such that a substantial portion of the surface of most of the filaments is covered with an almost continuous film of residue of the aqueous impregnating composition and most of the fibers are separated from each other. It is. The bundle need only be impregnated itself and need not be encapsulated in the impregnating composition. When the ethylene-containing interpolymer is present as an emulsion or dispersion containing about 50% solids, the viscosity of the aqueous impregnating composition ranges from about 5 centipoise when applied to a kissroll type coating to about 5 centipoise at room temperature. It is preferred to extend to about 10±5 centipoise for diecoating. The total solids content of the aqueous impregnation composition varies depending on the diameter of the filaments in the bundle. Finer diameter filaments have a higher surface area and require more total solids in the composition. Additionally, optional components of the aqueous chemical coating composition include one or more water-emulsifiable or water-dispersible waxes. There is a need for a type and amount of wax that is effective as an adhesion promoter for coating matrices applied to fabrics made from flexible bundles of single fibers. Additionally, it is the type and amount of wax that is effective to provide a screening effect against UV degradation when the fabric or polymer coated fabric is not protected from the weather or environment. Wax can also change the friction properties of the impregnated monofilament bundle. The wax or waxes are dispersed or emulsified in water with suitable emulsifiers, as is known in the art. The wax or waxes can also be included in the aqueous impregnating composition in a pre-emulsified or dispersed form. A preferred wax material is a microcrystalline wax material. A suitable commercially available example is Valeco Division, Petrolite Corporation, Tulsa, Oklahoma.
Polymekon SPPW-40 Microcrystalline Wax in its pre-dispersed form from the Polymekon Corporation - Bareco Division. The wax is
It is a hydrocarbon dispersion with a solids content of 40%. Another suitable example is Mobil Chemical.
Mobilcer Q Microcrystalline Wax by Chemical Company. This material is
It is an acid-type aqueous emulsion of microcrystalline wax with a melting point of 71℃ (160ん), the average particle size of the emulsion is 2 microns, and the solid content is 50.5
The emulsion density is 7.9 and the pH is 6.8. The amount of wax present in the coating composition is preferably at most about 5% by weight of the aqueous impregnating composition. Suitable solids and dispersants or emulsifiers with suitable HBL values known in the art may be used to help emulsify or disperse the wax in water. Aqueous impregnating compositions can also include one or more plasticizers that dissolve, emulsify or disperse in water. The plasticizer is added in an amount effective to provide the ethylene-containing interpolymer with a suitable plasticizer. The preferred amount of plasticizer in the aqueous impregnation composition is at most 5% by weight. Plasticizers are used to lower the Tg and obtain a more flexible bundle in cases where the Tg of the interpolymer does not provide adequate flexibility to the impregnated monofilament bundle. Suitable HLB known in the art
A suitable solvent, emulsifier or dispersant having a value is used to emulsify or disperse the plasticizer in water. These emulsifiers are nonionic, cationic,
Although any anionic emulsifier may be used, a particularly useful type is a nonionic emulsifier such as polyoxyalkylene sorbitan monolaurate, commercially available as Tween 21 emulsifier from ICI America. be. The plasticizer used is Stauffer Chemical.
Chemical) Phosflex 179-A
(Phosphlex 179-A) A fire retardant plasticizer such as xylene triphosphate, which is commercially available as a plasticizer, is preferred. This material has a specific gravity at 20℃/20℃
1.143, or a liquid with a concentration of 9.5 pounds per gallon, has a pour point of -17.8°C (0
〓), SUS viscosity at 37.8℃ (100〓) is 220, and COC flash point is 235℃ (455〓). Also, nonylated phenol phosphite
Phosphite chelators such as phosphite
chelator) is emulsified or dispersed in the aqueous impregnating composition, or added to the composition in its unemulsified or dispersed state. Suitable phosphorous acid chelators are available from Argus Chemical Corporation, Brucklin, New York.
Chemical Corporation) Mark
It is commercially available as 1178. This material has a specific gravity
0.99, with a volatility of 0%. Other types of commercially available plasticizers are Drapex
Epoxidized soybean oil such as 6.8. However, any other water-soluble, water-emulsifiable, or water-dispersible plasticizer known in the art can be used in amounts that effectively plasticize the ethylene-containing interpolymer. The aqueous treatment compositions may include diene-containing elastomeric polymers as well as the ethylene-containing interpolymers already mentioned. The diene-containing elastomer is water-dispersible or water-emulsifiable using a suitable solvent or emulsifier. Suitable solvents and emulsifiers are known in the elastomeric latex art. This elastomeric material can be used as a latex in an aqueous impregnation composition to provide a reduced moisture and partially cured aqueous impregnation composition with a desired flex modulus.
It is preferable that an effective amount is added to provide flexibility. The modulus of the aqueous impregnation composition at 100% elongation of the cast film is approximately 200 to 8000 psi.
and more preferably from about 800 to about 5000 psi. Such aqueous impregnating compositions provide desirable flexibility when impregnated into bundles of filaments and dehydrated and partially cured. The amount of elastomeric latex used is such that it does not consistently interfere with the compatibility of the ethylene-containing interpolymer with the polymeric matrix coating that coats any fabric made from a flexible bundle of single fibers. be. When the ethylene-containing interpolymer has a polar copolymer that reduces the noncrystallinity of the interpolymer or increases the Tg of the interpolymer, a diene-containing elastomeric latex must be present in the coating composition. Desirably, the diene-containing elastomeric latex contains essentially no vinylpyridine monomeric or repeating units in the polymer. Vinylpyridine stiffens the elastomer and unduly reduces the flexibility of the dehydrated, dried, partially cured monofilament bundle. Suitable non-exclusive examples of diene-containing elastomers are polybutadiene homopolymers, carboxylated styrene-butadiene copolymers or other non-self-crosslinking elastomers. Here, a material "without self-crosslinking" refers to a polymeric material that cannot perform intramolecular, ie, internal crosslinking, but performs intermolecular, ie, external crosslinking with other materials. Intermolecular crosslinking means that a portion of a molecule or polymer chain is crosslinked with a portion of another homologous molecule or chain. Here, "chain" means
Refers to the backbone chain of a polymer and its pendant groups. Suitable examples of elastomers without self-crosslinking properties include the following. (i) Elastomeric reaction products purified by reaction of 1,3-diene hydrocarbon monomers such as butadiene-1,3, (ii) isoprene, (iii) 2,3-dimethyl-1,3-butadiene ,2
- ethyl-1,3-butadiene, which forms a homopolymer alone and forms an interpolymer when mixed; (iv) an α-monoolefin having 3 to 20 carbon atoms, such as propylene, and ethylene; Ethylene-propylene obtained by intermolecular polymerization from dienes such as dicyclopentadiene, 5-ethylidene-2-norbolene, 1,4-hexadiene, and 5-methylene-2-norbolene by a conventional method.
diene rubber (EPDM), (v) nitrile rubber, such as nitrile butadiene latex, or (vi) copolymers of isobutylene containing some butadiene, isoprene or mixtures thereof, so-called butyl rubber. Other elastomers that can be used include chloroprene or neoprene. All of these elastomeric materials can be used in latex form. Diene-containing elastomeric latexes are included in aqueous impregnating compositions whenever the polar comonomers of the ethylene-containing interpolymer are vinyl chloride, carbon monoxide, and vinyl fluoride. When a polybutadiene homopolymer latex or similar material is used, the amount will range from less than 20% to more than 40% based on the ethylene-containing interpolymer in the aqueous impregnating composition. If it is less than 20%, it loses its advantage in flexibility as it approaches 0%. If it exceeds 40% by weight, it provides appropriate flexibility, but
The moisture content is reduced causing an increase in the stickiness of the dried partially cured monofilament bundle residue.
If no alternative means of reducing this stickiness are taken, the amount of polybutadiene homopolymer should not significantly exceed 40% in order to maintain the less sticky nature of the bundle. You must do so. To maintain less tacky properties of the film, the styrene units in the carboxylated styrene butadiene copolymer can be increased. For example, increasing the styrene units from 60% to 84% by weight is one way to reduce the stickiness of the resulting residue. A non-exclusive example of a commercially available diene-containing elastomeric latex that can be used is the one available from Goodyear Tire and Rubber.
Rubber) LPM-6290, with a total solid content of 43~
46%, pH 8-9.5, maximum viscosity 6000 centipoise (RFT1 at 20 rpm), maximum coagulation 0.05%, mechanical stability 55-75 mg, surface tension 58-74 dynes/cm, particle size 500-2000 Å, maximum gel It has the property of containing 25%. Other non-exclusive examples of elastomeric latexes that are not self-crosslinking include:
Direx latex manufactured by Polysar of Monaca, Pennsylvania.
55E (Dylex latex 55E) and carboxylated styrene-butadiene latex also made by Polycer. The former has volatile components of 49-51% by volume;
C ₇ H ₆ = contains CH ₂ , C ₄ H ₆ and CCHO ₂ . The latter is
Contains 84% styrene. The aqueous impregnating composition consisting of an ethylene-containing interpolymer, a self-crosslinking material, and water is a diene elastomer without wax, plasticizer, and certain polar comonomers in the ethylene-containing interpolymer, as previously described. It is not necessary to include all optional ingredients such as any pigments and/or dyes known in the art of textile dyeing. In the absence of an essentially vinylpyridine-free diene-containing elastomeric latex, an aqueous impregnating composition of ethylene-containing interpolymer, self-crosslinking material, and water may contain ammonium hydroxide as a crosslinking modifier, Preferably, it contains one or more dispersed waxes and one or more dispersed plasticizers. When an essentially vinylpyridine-free diene-containing elastomeric material is present in the coating composition, it is desirable to include only one of a dispersed microcrystalline wax and a dispersed plasticizer. Aqueous impregnating compositions can be obtained by adding all the components, either sequentially or simultaneously, to a predetermined amount of water plus suitable emulsifiers to emulsify or disperse all the components in water. In the case of materials that are not soluble in water, they can be added to the aqueous impregnating composition in advance at a pre-emulsification or pre-dispersion stage using a suitable solvent and an emulsifier with an HLB value well known in the field. desirable. moreover,
More preferably, a dispersed plasticizer and a dispersed wax are added to the dispersion of the ethylene-containing interpolymer. The self-crosslinking material in the aqueous medium is diluted and ammonium hydroxide is added to control the rate of crosslinking. This mixture consists of an interpolymer and a plasticizer and/or
or added to an aqueous mixture of waxes. Preferably, the diene-containing elastomeric material is added to the aqueous medium before the self-crosslinking material is added to the aqueous mixture of interpolymer and plasticizer and/or wax. The aqueous coating is further diluted with water until the aqueous impregnation composition has a volume with the total solids and viscosity required for the impregnated bundle of filaments. The aqueous impregnating composition is applied to bundles of sized filaments, including strands, bundles of twisted or untwisted yarns, and bundles of filaments. The filaments are sized during their formation process for protection and to make them compatible with hydrophobic materials. When the filaments are glass fibers, sizing is carried out using an aqueous sizing composition having at least one coupling agent and a protectant that renders the fibers less hydrophobic. The protective agent may be a water-soluble, water-dispersible or water-emulsifiable glass fiber lubricant, a water-soluble, water-dispersible or water-emulsifiable glass fiber film-forming polymer, and is known in the art. Any known coupling agent, glass fiber lubricant or glass fiber film forming polymer can be used. Preferably, the sized glass filaments are essentially free of starch-forming materials. As a suitable non-exclusive example of a starch-free aqueous sizing composition for glass fibers, a composition such as that disclosed in US Pat. No. 4,390,647 to Girgis may be used. Application is carried out by dip coating, die coating or other known processes for coating single fiber bundles. This may be accomplished, for example, by dipping the bundle of filaments in a bath containing an aqueous impregnating composition or by contacting the bundle with a kiss roll or other device that moves the bundle while in contact with the bundle. Die coating is also carried out by arranging a bundle of monofilaments to be pulled, pressed or packed through a fixed or adjustable orifice. According to this method, by opening the strand when it is immediately in front of the orifice, the innermost region of the glass fiber bundle is effectively exposed to the liquid impregnating agent in the container. can. By running the bundle under constant tension over a bar or other mechanism before it comes into contact with the impregnating agent, the single fibers in the bundle are spread out to maximum spacing and better impregnated. It can be realized. Sized filaments have a sizing composition that does not create excessive unity between the filaments when the filaments are assembled into groups or bundles. Therefore, when performing dip coating or die coating, the coating composition surrounds the group or bundle of filaments and can enter into the bundle.
The single fibers are separated from each other to some extent. The degree of impregnation is desirably such that each filament in the bundle or spun strand has a substantial surface portion covered with the aqueous impregnating composition. This causes the filaments in the bundle to separate from each other as the aqueous impregnating composition dries and partially cures. A bundle of single fibers treated with an aqueous impregnating composition is
When dry, it partially hardens and reduces the moisture content in the composition. Any method known in the art for curing crosslinked materials can optionally be used to dry and cure the impregnated monofilament bundle. Drying is done with a non-dielectric type, and the moisture content is approximately 1 to 1
Preferably, it is reduced to a range of about 2% or less. Moisture reduction and partial curing are achieved by drying at a suitable temperature and a suitable number of times. Drying is preferably carried out at a temperature in the range of about 200°C to about 260°C (400-500°C) for about 10 to about 60 seconds, resulting in the same degree of moisture reduction and the same degree of partial hardening. Other temperature and time relationships may be employed. The impregnated bundle of partially cured monofilaments is flexible enough to withstand a variety of fabric manufacturing methods.
Non-exclusive examples of woven fabric manufacturing processes include woven fabrics, non-woven fabrics,
knitted fabric, braided
Weft-knit fabrics produced on looms with Mayer or Libyan weft threads. In the method of producing this last type of woven fabric, the knitted fabric has a crosslaid warp and weft structure in both directions, but the weft is not interlaced as in conventional woven fabrics. .
A ``kint stitch'' is created in the vertical machine direction and tied into the fabric. When weaving textiles, plain weave, satin weave, and other weaving methods known in the art are used to make the woven fabric. Woven or non-woven, braided or braided fabrics can be provided with various types of coatings by various methods. Examples of suitable polymer coating materials include the following materials: Vinyl resins such as polyvinyl chloride, polyethylene, ethylene copolymers, polyurethanes, phenolic resins, melamine formaldehyde resins, elastomeric materials such as chlorosulfonated or chlorinated polyethylene, ethylene, propylene and dienes. Hypalon elastomers and silicone polymers. These types of polymers can be fabricated into single fibers by impregnation and saturation filling, surface coating methods such as solvent coating or 100% solids coating, or lamination with preformed films or sheets. It is coated on a cloth consisting of flexible bundles. For example, plastisol
When a 100% solids coating is performed, an initial coating of poly(vinyl chloride) latex is applied to the fabric to improve the viscosity of subsequent plastisol applications. After applying the plastisol coating paste to the fabric, the fabric is typically heated at 176-205°C (350°C) such that the resin particles form a continuous phase over the fabric and substantially bridge the gaps between the fabrics. ~400〓)
heated at a temperature of The polymeric coating is then cooled to form a tough, dense film at room temperature. The melting is so rapid that the coated fabric is cooled as soon as it reaches the required temperature. In addition to the polymeric material, various pigments and fillers may be used, and plasticizers and solvents may be used in place of the polymeric material. Coating with a polymeric coating, preferably polyvinyl chloride, is also applicable to other coating methods known in the art in which the fabric is passed over a knife-over-roll coater. Wet coating methods known in the art may also be used.
coating) can also be used. For example, the fabric may be passed through a knife coater one after the other or a floating knife coater in a support channel. In addition to this, there are also blankets.
A levlon coater with a knife coater, an inverted knife coater and a reverse smoothing roll is used as an engraved-roll or rotogravure coating unit. When using plastisols, any dry or 100% solids coating method known in the art can be used. Examples include hot melt coatings and other wet coating methods that do not involve evaporation of any solvent. Furthermore, a cast coating method or a method using a metal-belt precast coater can be used. Alternatively, dry powder resin coating methods such as hot calendar-coating or extrusion coating may be used. Furthermore, as in the case of mixed woven fabrics, a lamination method using a polymer film or sheet formed by a wet lamination method or a dry lamination method can also be used. In the lamination method, films or sheets are formed by calendering, extrusion or casting, respectively, and laminated to the fabric. These methods allow the plastic sheet to be coated with an adhesive prior to compressing the cloth and plastic sheet. That is,
The plastic sheet itself acts as a thermoplastic adhesive, becoming adhesive when heated and bonding to the hot cloth. This adhesion is achieved through a multiple-ply drum lamination process.
lamination process). Additionally, for foamable polymeric materials, a thermoplastic foam lamination process can be used. FIG. 1 depicts a coated fabric of the present invention. Reference numeral 12 designates a fabric consisting of an impregnated flexible bundle of monofilaments of the present invention, and reference numerals 11 and 13 indicate laminated polyvinyl chloride sheets or films sandwiching the fabric between the laminated sheets. The thickness of the coated fabric typically ranges from less than 0.025 cm (0.010 in.) to greater than 0.15 cm (0.06 in.), and the amount of coverage per unit area of fabric varies widely, but is usually about 170 in. ~1700 g/ ^m2 (5-50 oz/ ^yd2 ). Preferred embodiments of the invention are described below. The monofilaments may be of any fiberizable glass composition, such as "E-glass", "621-glass"
-glass, "C-glass" or "S-glass" and any derivatives thereof with low or no boron and/or fluorine. The most preferred glass composition is "621-glass". Glass fibers are formed by narrowing a stream of molten glass exiting an orifice in the bushing of a single glass furnace. After the filaments have been cooled below the boiling point of water, an aqueous sizing composition is added to the fibers. The aqueous sizing composition is a non-starch textile sizing agent.
size) and BASF Wyandot (BASF
A polyalkylene polyol commercially available as Pluracol V-7 polyol from Wyandotte and Pluracol V-10 polyol from Wyandotte.
It is a mixture of commercially available polyoxyalkylene polyols at a ratio of 50:50.
The amount of the mixture ranges from about 0.5 to about 5%, preferably from about 1 to about 3% by weight of the aqueous treatment composition.
is within the range of Preferably, the silane coupling agent is a lubricated aminosilane coupling agent commercially available as Y-9072 silane from Union Carbide. The amount of this coupling agent is
Within the range of about 0.01 to about 2% by weight of the aqueous treatment composition. Cationic lubricant is Emery 6760-U
Preferred is a polyamine lubricant available as an acidified fatty cationic amide (Emery 6760-U). The lubricant is present in the aqueous treatment composition in an amount of about 0.01 to about 4% by weight. The total solids content of the aqueous treatment composition may range from about 3% to about 20% by weight, although the total solids content may be within a range convenient for the sizing composition to be applied to the glass fibers at a suitable and desired LOI. It is preferable that It is desirable to apply the aqueous treatment composition to the glass fibers to provide an LOI in the range of about 0.1% to about 1%, preferably about 0.5% to about 0.8%. The glass fibers treated with the aqueous non-starch sizing composition are collected into one or more strands, preferably one strand. The diameter of the filaments ranges from less than 5 microns to about 30 microns, preferably from about 5 microns to 15 microns. The strands are collected for winding into a package and dried to reduce the water content of the aqueous sizing composition to about 0.1-1% by weight. One or more strands are coated with an aqueous impregnating composition having, for example, the following composition: Air Flex 410 10,000 g (vinyl acetate/ethylene copolymer, Air Products and Chemicals) Water 6,500 g Polymecon SPPW-40 400 g (microcrystalline wax, Petrolite Corporation's Valeco Division) Mark 1178 50 g (nonyl Phosphite phenol, Argus Chemical Company) Tween 21 50g (Polyoxyethylene sorbitan monourarate, ICI America, Inc.) Phosflex 179 500g (Xylene triphosphate, Stoffer Chemical Company) Myrj 52 75g (Polyoxy Ethylene Stearate, ICI America, Inc.) Regimen 500 g (Melamine Formaldehyde Resin, Monsanto Company) Direx D-55E 1000 g (Carboxylated SBR Latex, Polycer Company) Water Amount to give a solids content of 18% Aqueous sizing composition , PH8.5±0.5, viscosity 4~
It has 5 centipoise. The coating is alternatively preferably carried out by a die coating method or a dip coating method. The total solid content in the aqueous impregnating composition is about 8 to
About 35% by weight, preferably about 15-35% by weight. The coated fiber bundle is reduced in moisture and dried such that the aqueous impregnation composition has a viscosity of less than about 10 centipoise at room temperature. Drying temperature is 10~
Within the range of 218~260℃ (425~500〓) for 60 seconds. The amount of dip coating, i.e. impregnating, the bundle of single fibers is from about 4 to about 35% by weight depending on the fiber diameter of the glass fiber bundle, preferably about 9% by weight.
~30% by weight. The coated bundles are collected without twisting and woven into cloth. The fabric is coated with polyvinyl chloride plastisol during the calendering process. The cloth is initially made into a woven structure (weave
A very thin film of vinyl plastisol is coated with appropriate tension to set the structure. Along the coating line, approximately 0.05 to approximately 0.1 cm (0.02 to
Several passes were formed in the coated fabric to deposit a continuous film 0.04 inch thick. The coated fabric is heated to approximately 127°C (260°C) under pressure.
After being cured for several minutes at 〓), it is cooled to room temperature and wound up into a roll. Another embodiment of the invention is illustrated as follows. Table 1 provides data on the formation of aqueous coatings applied to 11 sized glass fibers. Single fiber diameter of glass fiber is approx.
It was 13 microns (K-fiber). The fibers were sized with 10 gallons of an aqueous sizing composition containing equal amounts, or 758 grams, of each of polyalkylene polyol V-7 polyol and polyoxyalkylene polyol V-10 polyol. The polyoxyalkylene polyol was diluted with stirring in warm deionized water to approximately 50% of the total water used for sizing. The hot water was prepared in a premix tank at about 60-71°C (140-160°) with stirring. The mixture was stirred for 10 minutes until it became clear and
The polyol was then added to the main mixing tank.
758g of polyalkylene polyol was added directly to the main mix tank. Deionized hot water in an amount of approximately 20% of the total water in the aqueous sizing composition
Approximately 290 grams of glass fiber lubricant was added to the premix tank and stirred for approximately 10 minutes. The mixture was transferred to the main mixing tank. 290 g of lubricated silane was added to the main mixing tank.
The aqueous sizing composition was diluted with deionized water to a final volume of 10 gallons, stirred for approximately 10 minutes, and then sampled. These fibers were treated by dip coating using the aqueous impregnating compositions listed in Table 1. The coated filament bundles were constructed as K-15 1/0 construction with 1000 filaments per bundle. In Table 1, Air Flex is used as an ethylene-vinyl acetate copolymer.
410 copolymer as ethylene-vinyl acetate-vinyl chloride terpolymer, Air Flex 728 terpolymer as ethylene-vinyl acetate-vinyl chloride terpolymer, and Petrolite Corp. as microcrystalline wax, marked as nonylated phosphorous phenol. Mark 1178 Argus was used, Tween 21 was used as the polyoxyethylene sorbitan monolaurate, and Phosflex was used as the xylene triphosphate. In addition to the strand structure of this example, strands of bundle structure G-75 5/0 can also be used. Due to its characteristics, G-fiber has a G-75 structure.
Each strand has a diameter of 9.53±0.63 microns
It is composed of 5 strands with 400 single fibers, and each bundle has 2000 single fibers. Also about
A single bundle having 3000 or more filaments can be impregnated and used as a flexible impregnated filament bundle of the present invention.

【table】

TABLE A number of yarns impregnated with the coating compositions of Table 1 were tested according to the contents of Tables 2 and 3. Table 2 shows the original sample, the sample stored at 49°C (120°C) and 98% relative humidity for 14 days and 28 days, respectively, and the 28
The results of a breaking strength test performed on a sample that had been soaked in water for several days according to a standard test method are shown. The numbers in the table represent breaking strength in pounds. Table 3 also shows how the MIT Flexure Folding Tester (MIT
Flex folding test)
The results of the resistance test are shown below based on the standard test method. Numbers in the table indicate failure.
It represents the number of cycles leading to . Unimpregnated fiberglass yarns sized with an aqueous sizing composition according to the preferred embodiment were tested for break strength and deflection properties at 35.5 psi and 60 cycles, respectively. Each sample tested in Tables 2 and 3 was kept at 26° C. (78°) and 55% relative humidity for 24 hours prior to testing to simulate certain storage conditions. For the flexure bending test in Table 3, 0.08 cm (0.03
mounting head (inch)
head), a load of 0.125 pounds was applied.
As shown in Table 3, it can be seen that the bundles of single fibers impregnated with the coating composition of the present invention have improved deflection properties.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a perspective view showing laminated sheets or films used for cloth and a covered cloth sandwiched therebetween. Reference numerals in the drawings: 11...Laminated sheets or films, 12...Covered cloth, 13...
Laminated sheets or films.

Claims (1)

Claims: 1. A flexible bundle of sized monofilaments coated and impregnated with a partially cured dry residue of an aqueous impregnation composition comprising components a, b and c of the following: . a Vinyl acetate, methyl acrylate, ethyl acrylate, styrene, α-methylstyrene, methyl methacrylate, acrylamide, methacrylic acid, n-methyl-N-vinylacetamide, diethyl fumarate, diethyl maleate, n-vinylpyrrolidone, and A water-dispersible or water-emulsifiable comonomer produced from one or more polar comonomers selected from the group consisting of n-vinylsuccinimide and present in an amount effectively compatible with the impregnating composition. an elastomeric ethylene-containing interpolymer; b a self-crosslinking material present in an amount effective to cause partial curing of the residue and reduce the tackiness of the residue on the surface of the coated bundle; c Water present in a predominant amount in an aqueous impregnating composition. 2. A flexible monofilament bundle according to claim 1, comprising an effective amount of a crosslinking modifier in the aqueous impregnating composition. 3. The flexible single fiber bundle according to claim 1, wherein the aqueous impregnating composition contains one or more water-emulsifiable or water-dispersible plasticizers. 4. Soybean oil in which the water-emulsifiable or water-dispersible plasticizer is epoxidized, xylene triphosphate emulsified with polyoxyethylene stearate,
The flexible single fiber bundle according to claim 3, which is nonylated phosphite phenol emulsified with polyoxyethylene sorbitan monolaurate. 5. The flexible single fiber bundle according to claim 1, wherein the aqueous impregnating composition contains one or more water-emulsifiable or water-dispersible microcrystalline waxes. 6. The flexible single fiber bundle according to claim 5, wherein the water-emulsifiable or water-dispersible microcrystalline wax is an aliphatic hydrocarbon wax in an aqueous medium. 7. The flexible single fiber bundle according to claim 1, wherein the aqueous impregnating composition has a total solids content and a viscosity of such an amount that the aqueous impregnating composition can effectively impregnate the bundle. 8. The flexible single fiber bundle according to claim 1, wherein the single fibers are glass fibers. 9. A flexible monofilament bundle according to claim 1, which is used in the form of a cloth coated with a polymeric material. 10 A bundle of single fibers containing the dry residue of an aqueous impregnating composition comprising at least one hydrophobic compatibilizer and a protective agent and comprising the following components a, b, c and d, the bundle comprising: A flexible monofilament bundle having at least one partially cured dry residue coated on the bundle and impregnated into the bundle. a water-dispersible or water-emulsifiable elastomeric ethylene-containing interpolymer consisting of one or more polar comonomers in a predominant amount based on the solids content of the dispersion; b self-crosslinking in an amount capable of effectively crosslinking. c. a water-dispersible or water-emulsifiable diene-containing elastomer; d. water present in a predominant amount in the aqueous impregnating composition. 11 the elastomeric ethylene-containing interpolymer is an ethylene vinyl acetate copolymer, the ethylene vinyl acetate copolymer comprising about 50 to 80% by weight vinyl acetate units;
and ethylene repeating units in an amount such that the glass transition temperature of the copolymer is about 0°C or less. 12. The flexible monofilament bundle of claim 10, wherein said elastomeric ethylene-containing interpolymer is present in a predominant amount of the solids content of the aqueous impregnating composition. 13. The flexible polymer according to claim 10, wherein the self-crosslinkable methylene donating condensation polymer is a resin selected from the group consisting of resorcinol formaldehyde resin, phenol formaldehyde resin, melamine formaldehyde resin, and mixtures thereof. Single fiber bundle. 14. The flexible monofilament bundle of claim 10, wherein said self-crosslinking methylene donating condensation polymer is present in an amount of from about 3 to about 10% by weight of the aqueous impregnating composition. 15. The flexible monofilament bundle of claim 10, wherein said diene-containing elastomer is a polymer selected from the group consisting of polybutadiene homopolymers and carboxylated styrene-butadiene copolymers. 16. The flexible monofilament bundle of claim 10, wherein said diene-containing elastomer is essentially free of vinylpyridine repeat units and is present in an amount of from about 5 to about 10% by weight of the aqueous impregnating composition. 17. The water provides a total solids content of about 8% to about 35% by weight in the aqueous impregnating composition and a viscosity of about 1.5% to about 10%.
11. A flexible monofilament bundle according to claim 10, present in centipoise amounts. 18. The flexible monofilament bundle of claim 10, wherein said aqueous impregnating composition includes one or more water-dispersible or water-emulsifiable waxes in an amount that effectively promotes adhesion. 19. The flexible single fiber bundle according to claim 10, wherein the aqueous impregnating composition contains a crosslinking modifier. 20. The flexible single fiber bundle according to claim 19, wherein the crosslinking regulator is ammonium hydroxide. 21. The flexible single fiber bundle according to claim 10, wherein the aqueous impregnating composition contains one or more water-emulsifiable or water-dispersible plasticizers. 22. The flexible single fiber bundle according to claim 10, wherein the single fibers are glass fibers. 23. A flexible monofilament bundle according to claim 10, which is used in the form of a cloth coated with a polymeric material. 24 A flexible glass fiber bundle composed of the following components a and b. a drying of an aqueous impregnating composition consisting of one or more coupling agents, one or more glass fiber protectants and water over a substantial portion of all the glass fibers in the bundle; b) a dried residue of a partially cured aqueous impregnating composition comprising the following components which coats and impregnates a bundle of glass fibers, the residue comprising a bundle of glass fibers; The first dry residue covers a substantial portion of the surface of most of the filaments in the second dry residue, the vinyl acetate comonomer is present in the copolymer at about 50-80% by weight, and the ethylene is in the copolymer. a water-emulsifiable or water-dispersible elastomeric ethylene vinyl acetate copolymer containing a water-emulsifiable or water-dispersible elastomeric ethylene vinyl acetate copolymer containing sufficient weight percent to reduce the glass transition temperature of the water to 0° C. or below; a water-dispersible or water-emulsifiable microcrystalline wax; one or more water-dispersible or water-emulsifiable plasticizers; a water-emulsifiable or water-dispersible diene selected from the group consisting of melamine formaldehyde resins, polybutadiene homopolymers and carboxylated styrene-butadiene copolymers; The elastomer contains water present in an amount to provide a total solids content of from about 8% to about 32% by weight and a viscosity of less than 10 centipoise at room temperature. 25. The flexible glass fiber bundle of claim 24, wherein at least one plasticizer in the aqueous impregnating composition is a fire retardant plasticizer. 26. Glass fiber bundle according to claim 24, used in the form of a cloth coated with a polymeric material.