JPS6197474A - Flexible chemically treated cloth and coated cloth - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to chemically treated fibers such as strands or yarns used in woven fabrics, which have particular application when coated or laminated to polymeric films. Regarding a bunch of.

[Prior Art] Chemically coated textiles are produced 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. Examples include synthetic rubbers such as neoprene and hypalon (■yl)alon@) rubber and nitrile rubber.

With the development of various polymeric film materials, textile materials including textiles have also advanced. For example, polyesters, polyamides like nylon, Kevlar
Examples include aramid fibers such as vlar@) 1Jift, rayon, graphite, glass fibers and other organic or inorganic man-made fibers.

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.
ure). There are also 425,000 m of clad fabric roofs for airport facilities and 26,000 T/l of air-supported clad fabric roofs for stadiums. On the other hand, examples of industrial and commercial applications include water storage, swimming pools, ponds, garbage disposal site covers,
It has a lining, sunshade or tarpaulin. 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. What about these required performances? li!
Some contributions are made by the uncovered fabric and the covering polymer film, and others are their combined contributions. The performance required from textiles includes tensile strength,
Flexibility, weather resistance, mulberry resistance, tear strength, resistance to tear spread.

tear propapation), dimensional stability to minimize elongation under load, stability under various humidity conditions, 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 MML materials used for polymer-coated textiles lack one or more of the above-mentioned required performances. For example, non-woven fabrics 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 films that are coated or laminated onto textiles. lacks adhesion to

Additionally, when fiberglass is used in the fabric to be covered, it is traditionally used as greige goods.
good) is used. The production of glass fibers typically involves applying an aqueous chemical treatment composition to a thin strip that flows out of the furnace bushing in which the glass was melted as a stream of molten glass.
ating composition). The single jlff is combined into a smealand and the strands are twisted or untwisted into a yarn. Greige goods are obtained by weaving 1m of glass yarn. The yarn is then thermally cleaned to remove the chemistry of the sizing composition. Thermal cleaning of the 83 mft of glass yarn reduces the inherent strength of the glass 11 sheet in certain aspects, thus attenuating the strength properties of the glass IIN fabric. 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 the tame material and polymer film in this way, the thickness is usually 1 mm 15! A coated fabric is produced with a total thickness of more than about 7,500 degrees per TIt. The polymeric film of the coated dishcloth provides airtightness, coloration and abrasion resistance to the cloth.

Even if organic m-string materials are used in the fabric, the chemical bond between the coating and the fabric is not very strong, despite the inclusion of adhesion promoters to the fabric in the polymeric composition that makes up the film. It's not a thing.

It is an object of the present invention to provide a flexible and abrasion resistant mu material, resulting in an improvement in coated or laminated textile products.

It is further an object of the invention to provide i! with improved flexibility and abrasion resistance. The object of the present invention is to provide an improvement in woven or non-woven fabrics that can be made into coated textile products without requiring heat treatment of the fiber material or fabric.

SUMMARY OF THE INVENTION It is an object of the invention set forth above and other objects of the invention that will become apparent from the description below to provide a reduced moisture and partially cured aqueous chemical treatment composition. This is accomplished by a bundle of sized single chicks, coated and impregnated with material residue. Aqueous chemical treatment compositions are water-soluble,
Dispersible or emulsifying elastomeric ethylene-containing interpolymers, such as copolymers or terpolymers made from ethylene monomers and one or more polar comonomers, and water-soluble, dispersing or emulsifying crosslinks. It is made of flexible polymer material. Ethylene-containing interpolymers have low glass transition temperatures of at most zero degrees. And to achieve this desired glass transition humidity,
One or more polar comonomers having sufficient ethylene segments to result in an essentially amorphous copolymer or terpolymer are included. 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 AAA bundle. In this impregnation, the water content of the aqueous impregnation composition is reduced and a partially cured residue is left behind in a few AA fl? Over a substantial portion of the bundle of ff, most single fibers are separated from each other to some extent f! The degree of impregnation present in i1 degrees.

The crosslinkable material is effective in causing some curing of the dehydrated residue of the coating to provide a substantially tack-free outer surface of the coated and impregnated monofilament bundle. present in the aqueous chemical treatment composition in an amount equal to

Aqueous chemical coating compositions include water-soluble, water-emulsifiable or water-dispersible waxes, plasticizers, diene-containing elastomers and crosslinking modifiers.
A controlling agent) can optionally be included. The latex of the diene-containing elastomer 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 raw fibers have dry 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 surface of the filaments more compatible with the hydrophobic coating. reduce sex.

The impregnated monofilament bundles are flexible enough to be woven into fabrics by themselves or with other monofilament bundles. The cloth is
Covered and hardened fabrics can be replaced by impregnation and saturation filling, surface coating with solvent-containing coatings or plastisols, and lamination with films or sheets of coating polymeric materials.

According to the invention, bundles of monofilaments, strands, rovings and bundles of twisted and untwisted strands and yarns having sufficient flexibility to be woven are Can be manufactured without the need to heat clean the bundles to remove chemical treatment agents.Typically, glass aj
When the iy is produced by conventional methods as a continuous single fiber, the single mH is processed in one process due to the rubbing and friction between the single ml, the contact between the single fibers and the eyes of the guide. It is treated with a sizing composition whose chemical composition protects it from the abrasions and abrasions that occur when cleaning. When weaving a fabric or cloth from a continuous 1111 or collection of strands or yarns, the yarns or warp threads running lengthwise in the fabric are separated from the moving parts of the loom. Easy to put away before considerable wear and tear. Wear on the warp yarns is caused by the guide surfaces of the loom's split rods (rsp++t rod), drop wires, confuser bars (c
onfuserbarS), heddle,
from the reed, shuttle and adjacent yarns.

To protect the warp yarns from such abrasion, slashing chemical compositions are commonly used. Once the cloth is woven, the woven fabric is
While the warp yarns have a sizing composition and a slashing sizing composition present from the time of formation, the weft yarns in the fabric only have the sizing composition from the time of formation. Additional coating of the warp yarns with a slashing sizing composition causes the warp yarns and weft 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 slashing sizing composition, and the yarns are incorporated into the dishcloth. For example, for glass fiber strand yarn fabrics, heat treatment is approximately 482-705°C (900-13°C).
0061”) for about 10 to 180 seconds or longer to evaporate the solids, remove them from the cloth, and remove them from the cloth.
Restore it and place it in its new position. Glass strands usually have good tensile strength, dimensional stability and resistance to chemical, photochemical and microbiological degradation. However, the heat treatment process attenuates some strength properties of the glass fiber strands.

Monofilaments such as polyamides such as polyester, nylon and Kevlar result in fabrics that are coated and laminated with polymeric films. Glass fiber strand yarns do not have the same flexibility as polyester or polyamide yarns.
erty) and low density. More flexible monofilament bundles, especially single glass IJ1M, strands, yarns, and even polyesters and polyamides can be made into the impregnated monofilament bundles of the present invention. The impregnated monofilament bundles have excellent fracture strength properties and flex fatigue resistance.
It has improved fatigue resistance, maintains these properties even after prolonged exposure to high humidity and water, and has good adhesion to the coating matrix of polymeric films.

The sized unit of the invention! The miscellaneous bundle has an impregnant that is the residue of a water-based impregnating composition that has been dehydrated and partially cured. The aqueous coating has a predominant amount of solids consisting of an elastomeric ethylene-containing interpolymer. Interpolymers are usually copolymers or terpolymers, but
It is formed from ethylene monomer and one or more polar comonomers. The comonomers can vary from eutectic with the poly'ethylene crystal structure to substantially amorphous interpolymers. Non-exclusive examples of these comonomers are vinyl acetate, methyl acrylate, ethyl acrylate, styrene, α-methylstyrene, methyl methacrylate, acrylamide, methacrylic acid, n-methyl-
N-vinylacetamide, diethyl fumarate, diethyl maleate, vinylpyrrolidone, n-vinylsuccinimide, and mixtures thereof.

The interpolymer has a ratio of ethylene to polar comonomer sufficient to provide a glass transition humidity (TO) of about θ° 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, 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. Homogeneous interpolymers are produced from two or more monomers of equal reactivity polymerized at any conversion, or when the monomers have different reactivities, the conversion is determined by intermolecular polymerization (interpo+ymer).
+zat+on) at low conversion rates such that the comonomer concentration remains nearly constant. Heterogeneous and alternating copolymers are known to those skilled in the art. The interpolymers may also be water-soluble, water-emulsifiable or water-dispersible with suitable emulsifiers and/or solvents. The interpolymer can be manufactured by conventional methods in the ethylene copolymer art. Particularly useful elastomeric ethylene-containing interpolymers include about 25 mole percent or more in the copolymer, or about 45 to 80 mole percent
Nib 1 is a non-vinyl acetate copolymer containing % by weight of vinyl acetate-1-monomer. The copolymer also has a TO of Oo of the copolymer of ethylene vinyl acetate.
Contains a sufficient amount of ethylene comonomer such that C or less. A non-exclusive example of an ethylene vinyl acetate-1-copolymer is available from Air Products & Chemicals, Inc.
ts and chemicals, Inc) air
airflexa 410 vinyl acetate-1-7/ethylene copolymer. The copolymer has the composition A, -By, where A is C4H6
02 and B represents C2H4. emulsion outside fi
1. ! is a white fluid liquid (mobile 1iquid)
Brookfield viscometer model 1. When measured with Vf' (25°C, 60 rpm spindle No. 2 or No. 3), 3.
5IJS viscosity at 7.8°C (100”F) is 100-2
．． It is 000. In addition, the emulsion has I)H of 4 to 7
The content of volatile components is 45 to 53% by volume, the specific gravity is 1.1, and the density is 9 bonds per gallon.

Aqueous dispersions have very small polymer particles in water, with 0
．． Contains up to 1141% formaldehyde and no other photochemically reactive or reactive chemical solvents are added. The remaining unpolymerized Nanatsuma darkness is 0.5% of the total amount.
less than The amount of ethylene-containing interpolymer in the aqueous impregnating composition is such that the amount of ethylene-containing interpolymer in the aqueous impregnating composition is sufficient to impregnate the single fiber bundle and form a nearly continuous film over a substantial portion of the surface of the filaments in the single fiber bundle. It is an effective sunny day. The amount is also an effective amount to form a film on a single IJi It bundle. Generally, the basis is that the solids content of the aqueous impregnating composition is predominant.

In addition to the ethylene-containing interpolymer, the aqueous chemical impregnation composition includes one or more crosslinking materials. Optimal crosslinking materials are suitable for use at ambient or elevated temperatures and atmospheric or sub-atmospheric pressures.
c pressure) or super atmospheric pressure (super
-atmosphertc pressure) and at least self-crosslinking property (self-crosslinkab).
le) compounds, monomers, oligomers and resinous polymers. Self-crosslinking means that the material does not need to be crosslinked with the ethylene-containing interpolymer. Polymer crosslinked materials are internally crosslinked (inter
nal crosslinkiH) or an external compound. External cross-linking (θxternal cross-linking
Sl inking 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,
Examples include polymers that are not rubbery polymers, such as polyisobutylene, styrene-butadiene-vinylpyridine turbosumers, and styrene-butadiene copolymers. Non-exclusive examples of crosslinked materials are melamine formaldehyde and condensates, monomers, dimers, trimers and higher oligomers, including hexakis/methylol. Furthermore, as phenol or resorcinol, cresol and mixtures of its isomers, xylenol or mixtures of its isomers, mixtures of homologs of phenols and dihydric phenols such as phloroglucinol, resorcinol, cresircinol, metaxylorcinol. The following compounds can be mentioned. Aldehyde includes any methylene donor used in place of formaldehyde. For example, paraformaldehyde, hexamethylenetetramine, acid aldehyde
ehyde), furfural and mixtures thereof. Aldehydes or methylol condensates are 1
．． Used with palliative or base catalysts. Internal hardening can also occur by removing stabilizing components.

For example, polyvalent metal ions are volatile rusting agents (vola
It is stabilized by the addition of tilecomplexing aOentS).

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 more than ff111 ammonia. 1 impregnation agent? Upon wiping, the ammonia evaporates, leaving a flexible, crosslinked impregnant.

This seedling is also used to deactivate the catalyst. 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. It is preferable to include one or more melamine formaldehyde resins because they are easy to crosslink and are compatible with ethylene-containing interpolymers. A particularly preferred melamine formaldehyde resin is an aqueous melamine formaldehyde resin containing less than 2x MM of formaldehyde, less than 5% methanol and 99°C (210"
F) Resimene 841 from Monsanto, which has a boiling point of F). Regimen 841 has methanol vapor pressure of 95 ml NO, water vapor pressure of 17.5 mmHo.

Methanol vapor density 1.11, water vapor density 0.6
4, has the appearance of a colorless and transparent flowing liquid, and has a temperature of 25°C.
(77'F), the specific gravity is 1.25, and the content of volatile components is 29% by volume.

The amount of crosslinking material in the aqueous impregnating composition is an effective amount to effect at least a partial curing of the water-reduced residue of the aqueous impregnating composition. Due to this partial hardening,
To control the surface tackiness due to the reduced moisture of residual impregnating agent, and to enable a bundle of impregnated single fibers to be almost uniformly rolled out from a wound package. If the bundle of filaments consists of filaments of larger diameter,
Partial hardening due to crosslinking can be reduced. When the filament bundle consists of ηjlJ fibers of smaller diameter, the partial hardening can be increased more than in the case of larger diameter filaments. When the impregnated bundles are densely packed with rolled up packages, the bundles become sensitive to stickiness and partial curing with a greater degree of crosslinking is preferred. Due to the controlled surface viscosity, the bundle of single ftjAH impregnated with the aqueous impregnating composition and reduced in moisture is incorporated into the culm of the loom using the feeder of the loom. Even if a feeder is used in the sti, the surface tackiness cannot be strictly controlled, so it may partially reduce curing. Preferably, partial curing achieves a reduced moisture hardness or modulus of the aqueous impregnating composition such that the flexibility of the impregnated single IJIhH bundle is improved by at least a factor of two. This improved flexibility exceeds that of a similarly made unimpregnated bundle of single fibers. In addition,
Partial curing causes further moisture-reduced curing of the aqueous impregnating composition impregnated into a single 111ff bundle.

This further hardening primarily results in bundles of single fmH and eventually impregnated single! Provides external adhesion to the polymeric film coating used on the fabric of the cord bundle. Also,
Furthermore, it produces an additional internal adhesive property of the zelkova, further promoting the integrity of the monofilament bundle achieved through partial curing. The limit for the spread of partial cure by crosslinking is the impregnated single Ti K(F
The flexibility of the bundle is less 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. The crosslinking modifier is something like ammonium hydroxide which changes the pH of the coating composition or an acid catalyst of the crosslinking material. A non-exclusive example of the latter includes American Cyanamid.
There is an isopropanol solution of toluene sulfonic acid commercially available as Cycat 4040 from IDE, which is 40% acid and 60% alcohol.

Additionally, in the absence of a crosslinking modifier, one of the monomers in the ethylene-containing interpolymer, depending on its concentration in the interpolymer, provides a less tacky film and increases the softening point of the interpolymer. The crosslinking modifier also helps control the hardness or modulus of the coated film. Frames used in aqueous impregnating compositions! ! ! The proportion of modifier varies depending on the strength of the modifier, but its Q 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 m of water, total solids concentration and viscosity of the composition provide a practical composition 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 of a certain degree. The bundle need only be impregnated itself and need not be enclosed in the impregnating composition.

If the ethylene-containing interpolymer is present as an emulsion or dispersion with a solids content of about 50'
The viscosity of the aqueous impregnating composition is determined by kissro
from about 5 centipoise when applied to ll) type coatings,
ng) to about 10±5 centipoise. The total solids content of the aqueous impregnating composition is the single I! Varies depending on the diameter of the piece. 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. A coating matrix adhesion promoter applied to a fabric made from a flexible bundle of single 4111
On promot Qr), effective type and amount of wax are required. Additionally, it is a type of wax that is effective in providing a screening effect against UV degradation when the fabric or polymeric coated fabric is not protected from the weather and environment. Waxes can also change the friction properties of impregnated monofilament bundles. 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. Commercially available examples include Oklahoma;
Petrolite Corporation's Baleco Division
on-Barec.

Polymecon (Pol Division) before dispersion
ymekon) SPPW-40v icrocrystalline wax. The wax is a hydrocarbon water dispersion with a solids content of 40%. Another suitable example is Hobil 1cer Q microcrystalline wax from Hobil Chem!cal. This material is an acidic aqueous emulsion of microcrystalline wax with a melting point of 71°C (160″F) and an average emulsion particle size of 2 microns.
Contains 50.5ml of solids, emery q
--To- 1 32 - The ulsion 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 in the wet 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 be dissolved, emulsified or dispersed in water11! ! Alternatively, it may contain two or more types of plasticizers. The plasticizer is added in an amount effective to impart appropriate plasticity to the ethylene-containing interpolymer. 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. Any suitable solvent, emulsifier or dispersant with a suitable elbow B value known in the art is used to emulsify or disperse the plasticizer in water. These emulsifiers may be nonionic, cationic, or anionic, but
A particularly useful type is ICI America (ICT^mer
A nonionic emulsifier such as polyoxyalkylene sorbitan monolaurate commercially available as Tween 21 emulsifier from ica. The plasticizer used is Stuffer ◆ly Mika/L/ (St
auffer C11emiC11e's Phosphlex 179e-A (Phosphlex 1796-A)
Fire retardant plasticizers such as xylene triphosphate, commercially available as nr plasticizers, are preferred. This material is heated at 20℃
Pour point at -17.8°C (0"F), 37.8°C + 100" at 10mm/11O pressure for liquid with a stopper of 1.143 or 9.5 bonds per gallon at /20°C.
F ) SUS viscosity rcJ220, COC flash point 23
The temperature is 5°C (below 455°C). In addition, nonylated phenol phos
Phosphite chelators (phosp) such as
or) 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 Arges, Pultuculin, New York.
Chemical Corporation (Argt+s Chem
icalcorporat 1on) mark (Mar
k) Commercially available as 1178. This material has a ratio of 7
It has a volatility of 40.99.0%. Other types of commercially available plasticizers include Ilrapex
6.8 is an epoxidized soybean oil. However, any other water-soluble, water-emulsifiable or water-dispersible plasticizer known in the art can be used to effectively plasticize the ethylene-containing interpolymer.

The aqueous treatment composition 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 desirable flex modulus.
It is preferable that an effective amount is added to make the material more flexible. 100% elongation of cast film of aqueous impregnating composition
tion) is approximately 200 to 8,0OOps.
i is preferably about 800 to about 5,0OOps
More preferably, it is i. Such aqueous impregnating compositions provide desirable flexibility when impregnated into bundles of filaments to reduce moisture and partially cure. 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. It is. When the ethylene-containing interpolymer is a polar copolymer that reduces the noncrystallinity of the interpolymer and increases the noncrystallinity of the interpolymer, the diene-containing elastomeric latex is present in the coating composition. Must exist.

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 moisture-reduced, 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. In this case, the term "chain" refers to the backbone chain of a polymer and its pendant groups.

Suitable examples of elastomers without self-crosslinking properties include the following.

(1) Elastomeric reaction products purified by reaction of 1,3-diene hydrocarbon monomers such as butadiene-1,3, (lI) isoprene, (t)2,3-dimethyl-1,3- Butadiene, 2-ethyl-1,3-butadiene, etc., which become homopolymers alone and become interpolymers when mixed, (b)
α- with 3 to 20 carbon atoms such as propylene
Ethylene-propylene obtained by intermolecular polymerization by a conventional method from monoolefin, ethylene, and dienes such as dicyclopentadiene, 5-ethylidene-2-norbolene, 1,4-hexadiene, and 5-methylene-2-norbolene. - diene rubber (IEPDH), (V) nitrile rubber, such as nitrile butadiene latex, or a copolymer of isobutylene containing 6, tD 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 latex is
When the polar comonomers of the ethylene-containing interpolymer are vinyl chloride, -carbon oxide and vinyl fluoride,
It is always included in aqueous impregnating compositions.

When a polybutadiene homopolymer latex or similar material is used, the amount will be within the range of less than 20% to more than 40% based on the ethylene-containing interpolymer in the aqueous impregnating composition. . 20
If it is less than %, as it approaches 0%,
You lose the advantage in terms of flexibility. If it exceeds 40% by weight, it will provide adequate flexibility but will cause an increase in the stickiness of the partially cured bundles of KN miscellaneous materials that have been dehydrated. If alternative means are not taken to avoid reducing this tackiness, the excitation of polybutadiene homopolymer can exceed much more than 40% in order to preserve the less tacky nature of the bundle. We must make sure that this does not happen. To preserve the less tacky nature of the film, increasing the styrene units in the carboxylated styrene butadiene copolymer can be avoided. For example, increasing the styrene units from 60% to 84% by weight is one way to reduce the tackiness of the resulting residue.

A non-exclusive example of a commercially available diene-containing nylastomer latex that can be used is Goodyear Tire and Rubbe.
r) Thank you LPH-6290, total solid content 43-46
%, pH 8-9.5, maximum viscosity 6.000 centipoise (RFTl at 20 ppm), maximum coagulation content 0.05%,
It has the following properties: mechanical stability of 55 to 75 mQ, surface tension of 58 to 74 dynes/cm, particle size of 500 to 2,000 dynes, and maximum gel content of 25%. Other non-exclusive examples of elastomeric latexes that are not self-crosslinking include Polysar latex 55F from Honaca, Pennsylvania, and carboxylated latex from Polysar, Inc. There is styrene butadiene latex. The former has volatile components of 49-51% by volume.
So, C7H6=CH2 and C4)16 and CCHO2 are included. The latter contains 84% styrene.

The aqueous impregnating composition comprising an ethylene-containing interpolymer, a self-crosslinking material, and water is a diene elastomer without waxes, plasticizers, and certain polar comonomers in the ethylene-containing interpolymer, as previously described.
It is not necessary to include all optional ingredients such as and any pigments and/or dyes known in the art of textile dyeing. In the absence of an essentially vinylpyridine-free diene-containing elastomeric latex, aqueous impregnating compositions with ethylene-containing interpolymers, self-crosslinking materials, and water may contain ammonium hydroxide as a crosslinking modifier. , one or more dispersed waxes, 1 Pm or two 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 the following: a dispersed microcrystalline wax and a dispersed plasticizer.

Aqueous impregnating compositions can be prepared by adding all components, either sequentially or simultaneously, to a predetermined amount of water plus a suitable emulsifier to emulsify or disperse all 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 this field. desirable. Furthermore, it is more desirable that 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 further comprises a single liter of the aqueous impregnating composition.
Boil with water until the container has the total solids content and viscosity required for a JN impregnated bundle.

The aqueous impregnating composition is applied to sized single mtitt bundles, including strands, twisted or untwisted yarn bundles, and single fiber bundles. Single tMM
is sized at its formation one culm for protection and to make it compatible with hydrophobic materials. When the single fiber is glass fiber, the sizing includes at least one coupling agent and a protective agent (p
This is done using an aqueous sizing composition with a sizing agent (rotectorant). The protective agent is water-soluble, water-dispersible or water-emulsifiable glass! It may be a fiber lubricant,
Any coupling agent, glass mmt lubricant or glass woven film-forming polymer known in the art may be used, which may be a water-soluble, water-dispersible or water-emulsifiable glass-woven film-forming polymer. I can do it.

Preferably, the sized glass unit Ill is essentially free of starch-forming materials.

As a preferred non-exclusive example of a starch-free aqueous sizing composition for glass fibers, Girai
Compositions such as those disclosed in U.S. Pat. No. 4,390,647 by S. Application is carried out by dip coating, die coating or other known methods of coating a single 1M bundle. For example, this may be accomplished by dipping the bundle of monotIA miscellaneous into a bath containing an aqueous impregnating composition or by contacting a kiss roll or other device that moves the bundle while in contact with the bundle. Die coating can also be done by pulling a bundle of *** through a fixed or adjustable orifice.
This is done by being placed in a pressed or packed manner.

This method effectively exposes the innermost regions of the glass fiber bundle to the liquid impregnating agent in the container by listening to the strand once it is just in front of the orifice. Before the bundle comes into contact with the impregnating agent,
By riding over a bar or other mechanism under constant tension, the single fibers in the bundle can be spread out to maximum spacing and better impregnation can be achieved. Sized filaments have a sizing composition that does not result in excessive unity between the filaments when the filaments are assembled into groups or bundles. Thus, when dip-coating or die-coating, the filaments are spaced apart from each other to some extent so that the coating composition can surround and enter the group or bundle of filaments. The degree of impregnation is preferably such that each single 11i1f in the bundle or spun strand has a substantial surface portion covered with the aqueous impregnating composition. By doing this, once the aqueous impregnating acid composition dries and partially hardens, the single fibers in the bundle 1 [
begin to move away from each other.

When a bundle of filaments treated with an aqueous impregnating composition dries, it partially hardens and the moisture in the composition is reduced. Any method known in the art for curing crosslinked materials can optionally be used to dry and cure the impregnated single L5Ii web bundle. Preferably, the drying is of the non-dielectric type and the moisture is reduced to a range of about 1 to about 2% or less of the bundle. 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. (below 400-500° C.) for about 10 to about 60 seconds, but may also achieve the same degree of moisture reduction and the same degree of partial hardening. Other temperature and time relationships may also be used.

The partially cured single 11ft impregnated fabric is flexible enough to withstand a variety of fabric manufacturing methods. A non-exclusive example of a method of manufacturing a woven fabric is a woven fabric.
ric), non-woven fabric
), knitted fabric, knitted fabric (
braided fabric) and Maye
r) Insert the weft thread of Oribiya (ljbVa)
Weft-knit fabric manufactured by
bric). In the method of manufacturing this last type of woven fabric, the hem fabric is crossed in both directions (cr6ssl
aid) It has a warp and weft structure, but the weft is
Like traditional woven fabrics, interlace
e) Not done. "Knit stitch (kint 5tl)
tch) J is made in the vertical machine direction and tied to 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 coated in various types by a variety of methods.

Examples of suitable polymer coating materials include the following materials: i.e. vinyl resins such as polyvinyl chloride, polyethylene, ethylene copolymers, polyurethanes, phenolic resins, melamine formaldehyde resins, elastomeric materials such as chlorosulfonated or chlorinated polyethylene, ethylene. , polymers consisting of propylene and diene monomers, Hypalon 0 elastomers and silicone polymers.

These types of polymers can be fabricated into single strands 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, when coating with plastisol 100x solids 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 between 176°C and 205°C so that the particles of resin are in a continuous phase over the fabric and substantially bridge the gaps between the fabrics. (350-400'l'').

The polymeric coating is then cooled to form a tough, dense film at room temperature. The melting is so rapid that the cloth is cooled as soon as the coated flT reaches the required temperature. In addition to polymeric materials, various pigments and fillers
RL may be used, and plasticizers and solvents may be used in place of the polymeric material.

The polymeric coating, preferably polyvinyl chloride, is
Knife-over roll coater (knife-ov)
Other coating methods known in the art are also applicable. Also, wet coating methods known in the art can be used. For example, by passing the fabric through a knife coater one after another or by passing the fabric through a support channel.
Knife coater (floating)
This method is similar to passing it through a knife coater.

Additionally, there are blanket knife coaters, inVerted knife coaters and reverse smoothing coaters.
level coater (level
on coater) is engrave trol (eng
raved-roll) or rotogravure coating unit
ng unit). When using plastisols, any dry or 100x hard coating methods known in the art can be used. For example, hot melt coating is a wet coating method that does not involve any solvent. In addition, cast coating method and metal-belt precast coater (metal-belt precast coater)
A method according to precaSt coater) can be used. In addition, hot calender coating (h
Dry powder resin coating methods such as otca+endar-coat+ng) methods and extrusion coating methods may also be used. Further, as in the case of mixed woven fabrics, it is also possible to use a polymeric film or sheet formed by a wet lamination method or a dry lamination method.

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 behaves like a thermoplastic adhesive on its own, becomes adhesive when heated, and bonds to the cloth while it is hot. This adhesion is achieved through the multilayer drum lamination process (mu
ltiple-ply run+ Iaminatt
on-process). In addition, for polymeric materials that can be foamed, thermoplastic foam lamination processes are used.
s) can be used.

FIG. 1 depicts a coated fabric of the present invention. (12
) shows a fabric consisting of a flexible bundle containing single 11M of the present invention, and (11) and (13) show vI layered polyvinyl chloride sheets or films sandwiching the fabric between laminated sheets. . Usually the thickness of the covered cloth is 0.0
From 25 cm (0,010 inch) to 51 - still smaller to 0.15 cm (0,06 inch)
Over a larger range, the amount of coverage per unit area of fabric varies widely, but VFI connoisseurs range from about 170 to about i7oo
g/day (5 to 50 oz/yd2).

Preferred embodiments of the invention are described below. Single IN can be any AI fiberizable glass composition, such as "E-glass J", "621-glass (621-
glassN, IJiM consisting of "C-olass J" or "S-Glass J" and any derivatives thereof with low or no boron and/or fluorine. The most preferred glass composition is It is "621-Glass".

Glass m M is formed by narrowing a molten stream of glass exiting an orifice in the bushing of a single glass furnace. After the filaments are cooled below the boiling point of water, an aqueous sizing composition is added to the IIN. The aqueous sizing composition includes a non-starch textile 5ize
) and BASF Wyandotte (BASF Wya
Pluracol V-7 polyol (Pl
uracol V-7polyol) and the company's Puracol V
-10 polyol (Pluracol V-10pol
yol) and a commercially available polyoxyalkylene polyol in a ratio of 50:50.

The amount of the mixture is from about 0.5 to about 5% by weight of the aqueous treatment composition.
and preferably from about 1 to about 3% by weight. The silane coupling agent is union carbide (U
Y-9072 silane (Y
Preferably, it is an aminosilane coupling agent with added lubricant commercially available as A-90725ilane). The amount of coupling agent ranges from about 0.01 to about 2% by weight of the aqueous treatment composition. The cadion lubricant is Emery 6760-u (Emery6760-u)
Polyamine II available as an acidified fatty cationic amide of! Preferably, it is a lubricant.

The lubricant is present in the aqueous treatment composition from about 0.01% to about 4% by weight. The total solids content of the aqueous treatment composition may be in any range convenient for the sizing composition to be added to the glass m-string at the appropriate and desired LOT, but the total solids content may be approximately 3.
Preferably, it is within the range of about 20% by weight. For glass Ili chicks, from about 0.1 to about 1%, preferably from about 0.5 to about 1%.
aqueous treatment to give a LOT in the range of about 0.8%]
! l! It is desirable to add a composition.

The glass fibers treated with the aqueous non-stirizing compound are assembled into one or more strands, preferably one strand. The diameter of single fibers ranges from less than 5 microns to IJ30 microns,
Preferably it is within the range of about 5 microns to 15 microns. The strands are collected for winding into a package and dried to reduce the moisture content of the aqueous sizing composition to about 0.1-1 digit percent. Type 1 or 2) [! The above strands are coated with an aqueous impregnating composition having, for example, the following composition.

Air Flex 410 10.000g (
Vinyl Acetate/Egielene Copolymer, Air Products & Chemicals, Inc.) Water
6,500 (] Bolimecon 5PPW-40400 (
] (Microcrystalline wax, Valeco Division of Petrolite Corporation) Mark 1178 50 (](
Nonylated raw soybean acid phenol, Alges Chemical Co.) Tween 21 50G (polyoxyethylene solgotan monolaurate, ICI America, Inc.) Phosflex 179 500IJ (xylene triphosphate, Stoffer Chemical Co.) Hyrj 52 75
0 (polyoxyethylene stearate, ICI America Inc.) Regimen 500g (melamine formaldehyde resin, Sensan 1- Inc.) Direx 1l-55E 1,
OOOg (Carboxylated SBR Latex, Polyzar) Water Amount to give 18% solids Aqueous sizing composition, pH 8.5 ± 0.5, viscosity 4
It has ~5 centigrade voids.

The coating is alternatively preferably carried out by die-coating or dip-coating. The total solids content in the aqueous impregnating composition is from about 8 to about 35% by weight;
Preferably it is about 9-30% by weight.

Covered 1! The shoe bundle is reduced in moisture and dried such that the aqueous impregnating composition has a viscosity of about 10 centimeters at room temperature. The drying time is 21 in 10-60 seconds.
within the range of 8 to 260°C (425 to 500”F).Dip coating into bundles of single Ill 56 = Dip coating, i.e., the amount of impregnation into bundles, depends on the mm diameter of the bundle. from about 4% to about 35% by weight, preferably from about 9% to 30% by weight.The coated bundles are collected without twisting and woven into a fabric.

The fabric is coated with polyvinyl chloride plastisol in a calendering culm. Cloth initially has a woven structure (wea
ve 5structure) is coated with a very thin film of vinyl plastisol, with appropriate tension to set the structure. Add about 0.05 to about 0.1 cm (0.02 cm) of polyvinyl chloride polymer along the coating line.
Several passes are made in the coated fabric to deposit a continuous film .about.0.04 inches thick. The coated fabric was heated to approximately 127°C (260') under pressure.
1") for several minutes, then cooled to room temperature and wound up into rolls.

Another embodiment of the invention is illustrated as follows.

Table 1 lists data regarding the formation of aqueous coatings applied to 11 sized glass fibers. The diameter of the glass fiber upper weave is approximately 13 microns (-
fiber).

The 41 string was sized with 10 gallons of aqueous sizing compound containing equal amounts, or 758 grams, of each of polyalkylene polyol L7 polyol and polyoxyalkylene polyol V-10 polyol. The polyoxyalkylene polyol was diluted with stirring in warm deionized water to about 50% of the total water used for sizing. The dry water temperature is approximately 60-71℃ (140℃) in the premix tank.
The mixture was stirred for 10 minutes until clear and then the polyol was added to the main mix tank. The 758Q polyalkylene polyol was added directly to the main mix tank.

Deionized warm water in an amount of about 20x of the total water of the aqueous sizing composition was added to the premix tank, about 2900 g of glass sizing lubricant was added, and stirred for about 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 1112 ionized water to a volume of 10 gallons, stirred for approximately 10 minutes, and then sampled. These ul
M was treated by dip coating using the aqueous impregnating composition shown in Table 1. The bundle of coated single fibers has 1,000 t3i [4 fibers per bundle]
It was constructed as a 15110 structure.

In Table 1, AirFIeX 410 copolymer is used as the ethylene-vinyl acetate copolymer, AirFIeX 728 terpolymer is used as the ethylene-vinyl acetate-vinyl chloride terpolymer, and Petroltte Corp. is used as the microcrystalline wax.
, ) manufactured by Mark 1178 Argues (Mark 1178^rgu) as nonyl raw bean phosphate phenol.
s), polyoxyx tyrene sorbitan monolaure-1
- Tween 21 as xylene triphosphate and Phosf te as xylene triphosphate.
x) was used.

In addition to the strand structure of this example, bundle structure G-75
510 strands can also be used. G-
[11 Silk has a diameter of 9.53 to 0.63 microns in its characteristics - G-75 structure, and each strand is composed of 5 strands with 400 single fJ l't. , with 2.000 single m lft in one bundle. Alternatively, a single bundle having about 3,000 or more filaments may be impregnated to form a flexible impregnated monofilament of the present invention.
It can be used as M bundle.

CLJ, bottom margin] -A9- 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, 49°C (120”F)
) under 98% relative humidity for 14 days and 2 hours, respectively.
Breaking strength tests were conducted on samples that had been left in water for 8 days and samples that had been soaked in water for 28 days.
The results of the strength test are shown below based on the standard test method. The numbers in the table represent breaking strength in pounds. Table 3 also shows the original sample, 28 days at 49°C (120”F) 9
Samples smelled at 8% relative humidity and samples soaked in water for 28 days were tested using a HIT flex folding tester (HIT flex folding tester).
flex resist test using
ance test) based on the standard test method. Numbers in the table indicate failure.
It represents the number of cycles leading to . Glass shoulder 1, unimpregnated yarn sized with an aqueous sizing composition as per the preferred embodiment was tested for breaking strength and deflection properties with a rating of 3.
It was 5.5 psi and 60 cycles. Each sample tested in Tables 2 and 3 was tested for 24 hours and 2 hours prior to trial run to simulate certain storage conditions.
It was maintained at 6°C (78"l") and 55x relative humidity. Third
The table flexure bending test uses 0,
A load of 125 bonds 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.

Margin below r]

[Brief explanation of drawings]

FIG. 1 is a perspective view showing laminated sheets or films used for fabric and a covered fabric sandwiched therebetween. (Drawing code) (11): Laminated sheet 1~ or film (12): Covered cloth (13): Laminated sheet or film Patent Applicant PPG Ingis 1-Leeds
4 Agents of Incorporated 540 5 Date of amendment order October 29, 1985 (shipment date) 6 Subject of amendment (1) Drawings 7 Contents of amendment (1) Engraving of drawings (no change in content) 8 List of attached documents (1) 1 drawing - Cr.

Claims (1)

[Scope of Claims] 1. Preparation of sized single fibers coated and impregnated with a dehydrated and partially cured residue of an aqueous impregnating composition comprising components a, b and c as follows: A flexible bundle. a, vinyl acetate, methyl acrylate, ethyl acrylate, styrene, α-methylstyrene, methyl methacrylate, acrylamide, methacrylate, 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 said residue and to reduce tackiness of said residue on the surface of said coated bundle; c Water present in a predominant amount in the 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, or nonylated phosphorous acid emulsified with polyoxyethylene sorbitan monolaurate. The flexible monofilament bundle according to claim 3, which is phenol. 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. Claim 1, wherein the single fiber is glass fiber.
Flexible monofilament bundle as described in Section 1. 9 A bundle of single fibers having a dehydrated 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. A flexible monofilament bundle, the bundle having at least one partially cured, moisture-reduced residue coating the bundle and impregnating 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 an effectively crosslinkable amount of self. a crosslinkable methylene donating condensation polymer; c a water-dispersible or water-emulsifiable diene-containing elastomer; d water present in a predominant amount in the aqueous impregnating composition. 10 the elastomeric ethylene-containing interpolymer is an ethylene vinyl acetate copolymer;
Claim 9, wherein the ethylene vinyl acetate copolymer contains about 50 to 80% by weight vinyl acetate units and contains ethylene repeat units in an amount such that the glass transition temperature of the copolymer is about 0°C or less. flexible monofilament bundle. 11. The flexible monofilament bundle of claim 9, wherein said elastomeric ethylene-containing interpolymer is present in a predominant amount of the solids content of the aqueous impregnating composition. 12 The self-crosslinking methylene donating condensation polymer is
The flexible monofilament bundle according to claim 9, which is a resin selected from the group consisting of resorcinol formaldehyde resin, phenol formaldehyde resin, melamine formaldehyde resin, and mixtures thereof. 13. The flexible monofilament bundle of claim 9, wherein said self-crosslinking methylene donating condensation polymer is present in an amount of about 3 to about 10% by weight of the aqueous impregnating composition. 14. The flexible monofilament bundle of claim 9, wherein said diene-containing elastomer is a polymer selected from the group consisting of polybutadiene homopolymers and carboxylated styrene-butadiene copolymers. 15. The flexible monofilament bundle of claim 9, wherein said diene-containing elastomer is essentially free of repeat units of vinylpyridine and is present from about 5 to about 10% by weight of the aqueous impregnating composition. 16 The water reduces the total solids content in the aqueous impregnating composition to about 8
10. The flexible monofilament bundle of claim 9 present in an amount to provide ~35% by weight and a viscosity of approximately 1.5 to 10 centipoise. 17. The flexible monofilament bundle of claim 9, wherein said aqueous impregnating composition comprises one or more water-dispersible or water-emulsifiable waxes in an amount that effectively promotes adhesion. 18. The flexible single fiber bundle according to claim 9, wherein the aqueous impregnating composition contains a crosslinking regulator. 19. The flexible single fiber bundle according to claim 9, wherein the crosslinking regulator is ammonium hydroxide. 20. The flexible single fiber bundle according to claim 9, wherein the aqueous impregnating composition contains one or more water-emulsifiable or water-dispersible plasticizers. 21. The flexible single fiber bundle according to claim 9, wherein the single fibers are glass fibers. 22 A flexible glass fiber bundle composed of the following components a and b. a. over a substantial portion of all the glass fibers in the bundle an aqueous impregnating composition consisting of one or more coupling agents, one or more glass fiber protectants and water; a multiplicity of glass fibers with a reduced moisture residue; b. an aqueous impregnation consisting of components i to vi of the following, reduced in moisture and partially cured, coating and impregnating the bundle of glass fibers: a residue of a composition for use, wherein the residue is a first moisture-depleted residue covering a substantial portion of the surface of most of the filaments in the bundle with a second moisture-depleted residue; i vinyl acetate comonomer in the copolymer
a water-emulsifiable or water-dispersible elastomeric ethylene vinyl acetate copolymer containing from 0 to 80% by weight and containing a sufficient weight% of ethylene to lower the glass transition temperature of the copolymer to 0° C. or below, ii from water-dispersible or water-emulsifiable microcrystalline waxes, iii. one or more water-dispersible or water-emulsifiable plasticizers, iv. melamine formaldehyde resins, v. polybutadiene homopolymers and carboxylated styrene-butadiene copolymers. a water-emulsifiable or water-dispersible diene-containing elastomer selected from the group consisting of vi water present in an amount to provide a total solids content of from about 8 to about 32 weight percent and a viscosity of less than 10 centipoise at room temperature; 23. The flexible glass fiber bundle of claim 22, wherein at least one plasticizer in the aqueous impregnating composition is a fire retardant plasticizer. 24. A polymer-coated fabric made of glass fibers according to claim 22. 25. A polymer-covered fabric composed of a bundle of single fibers according to claim 9. 26. A polymer-covered fabric composed of a bundle of single fibers according to claim 1.