Ppg Industries, Inc.

Peter C Gaa

Robert G Swisher

Jerry C Hedden

James W Kasunic

David E Dana

Narasimhan Raghupathi

H Kenyon Watkins

Mikhail M Girgis

Balbhadra Das

Donald L Motsinger

Johnson C Watkins

R Alan Davis

Fibrous material including fibers, bundles of fibers, strands, roving, flakes and beads have a dried residue of a chemical treating composition for improved solvent resistance of polymers the fibrous materials reinforced. The chemical treated composition has at least one crosslinkable polyurethane, at least one organofunctional silane coupling agent, and acrylic copolymer with at least one addition polymerizable acrylic-type monomer and at least one monomer that is addition polymerizable and matrix resin miscible and reactable and a carrier. In addition, the chemical treating composition can have a polyurethane crosslinking agent in an effective amount to produce a dried residue of limited swellability from the chemical treatment, where the residue is a thin film on a substantial portion of the surface of the fibrous materials. Optionally, there may be present at least one low temperature antioxidant such as alkali metal and alkaline earth metal hypo or hydrogen phosphites. Also, there may be present in addition or in lieu of the first antioxidant a high temperature antioxidant such as: alkali metal or alkaline earth metal phenylphosphonates, thioethers like dialkyl thioalkylionate and processing aids such as epoxy polyester polymers.

Chemical treatment for fibers and reinforcement for polymer matrices

Flexible coated bundles of fibers are provided that are both encapsulated and impregnated with a coating of one or more independently partially crosslinkable polyurethane. The fibers in the bundle can have a first chemical treatment or size and the bundle of these fibers is treated to have the coating of the polyurethane. The coating impregnates the bundle so that a majority of the fibers have a substantial portion of their surfaces covered with the coating. The independently partially crosslinkable polyurethane is selected from polyurethane polymers that are solvent-soluble, dispersible or emulsifiable that produce a thermoplastic elastomeric film. The partial crosslinkability is from one or more of the following types of crosslinking: self-crosslinkable, internally crosslinkable and/or in-situ crosslinkable. Additional components other than external crosslinking agents can also be present in the coating composition.

Impregnated fiber bundles having independently crosslinkable polyurethane

Chemically treated fibers of glass, carbon or polyamide have a treatment incorporating a copolymer or terpolymer with (vinylpyrrolidone-acrylate or acrylic moieties. In addition the treatment can have at least one film forming polymer, at least one organic/inorganic coupling agent, at least one fiber lubricant and water all in effective amounts to perform their stated functions. In one aspect of the invention the fibers are glass fibers which have a chemical treatment which is a dried residue of an aqueous chemical treating composition comprising at least one epoxy polymer, emulsion or dispersion in a predominant amount on a nonaqueous basis of the dried components amount of the aqueous chemical treating composition, at least one amino organofunctional silane coupling agent in an effective coupling agent amount, at least one cationic fiber lubricant in an effective lubricating amount and water. In this aspect the ratio of the epoxy to copolymer should be less than around 60 to 1.

Chemically treated glass fibers with improved reinforcement properties

Polymeric-containing compositions having improved oxidative stability have the polymer and at least two stabilizing agents. The composition can be a coating composition for substrates including those like fibrous material including fibers, bundles of fibers, strands, roving, flakes and beads. The composition can be present as a dried residue on the substrate. For Fibrous substrates, the composition also has at least one organofunctional silane coupling agent, may also have processing aids such as epoxy polyester polymers and/or lubricants. In addition, the polymeric-containing composition can have a crosslinking agent in an effective amount to produce a dried residue of limited swellability from the composition.

Polymeric-containing compositions with improved oxidative stability

Polymeric-containing compositions having improved oxidative stability have the polymer and at least two stabilizing agents. These agents are selected from low temperature antioxidants such as alkali metal and alkaline earth metal hypo or hydrogen phosphites, high temperature antioxidants such as: alkali metal or alkaline earth metal phenylphosphonates, thioethers like dialkyl thioalkylionate and polymers thereof and metal deactivating agents like polydentate ligands and ethylene diamine-tetracidic acid compounds. The composition can be a coating composition for substrates including those like fibrous material including fibers, bundles of fibers, strands, roving, flakes and beads. The composition can be present as a dried residue on the substrate. For fibrous substrates, the composition also has at least one organofunctional silane coupling agent, may also have processing aids such as epoxy polyester polymers and/or lubricants. In addition, the polymeric-containing composition can have a crosslinking agent in an effective amount to produce a dried residue of limited swellability from the composition.

Chemically treated glass fibers of the present invention perform well as wet chopped strands of glass fibers and are useful in producing glass fiber paper. In one aspect the chopped strands of glass fibers have an aqueous chemical treatment comprised of at least one water soluble, ungelled polymer having an effective viscosity, an effective film-forming capability and an effective molecular weight. In another aspect the chemically treated glass fibers have a chemical treating composition having a polyoxyethylene polymer as the water soluble and ungelled polymer with an effective film forming molecular weight along with water soluble, dispersible or emulsifiable aldehyde-condensate-reactable, polymeric agent, cationic lubricant or lubricating surfactant, aldehyde-condensate-reactable organo silane coupling agents and a carrier like water. The amount of the reactable polymeric agent is an effective white water compatible amount, where this agent is a polymer like either polyacrylamide or polyamide or a mixture of these. The aldehyde-condensate-reactable organo silane coupling agent can be an alkoxylated gamma aminoalkyltrialkoxy silane, a polyamino organo silane, mercapto functional organo silane or a ureido functional organo silane or a mixture thereof.

Treated glass fibers and aqueous dispersion and nonwoven mat of the

Treated glass fibers having adequate protection for gathering into strands and when chopped being more dispersible in aqueous media. The treated glass fibers have a coating of an aqueous treating composition, wherein the solids have a cationic surfactant having one or more primary, secondary and/or tertiary amine moieties and one or more water dispersible, poly(oxyethylene-oxyalkylene) copolymer having an oxide ratio of about 78 to about 22 to about 99 to about 1 and an average molecular weight of at least 15,000, and one or more polar functional coupling agents. Optionally, the solids may also have one or more starches that are insoluble or only incompletely soluble in cold water. Glass fibers treated with the aqueous treating compositions and produced into wet or dry chopped glass fiber strands having lengths of about 1/16 of an inch (1.58 mm) to about 3 inches (76.2 mm), have good dispersibility in aqueous media with or without addition of dispersing agents. Nonwoven, sheet-like mat is produced from aqueous dispersions having the chopped treated glass fibers, where some of the water is removed and polymeric binders, commonly referred to as wet strength binders, are applied and the mat is cured. The resulting nonwoven, sheet-like mat product has very good strength properties for use as a reinforcing element for roofing products, construction products and flooring products.

Treated glass fibers having adequate protection for gathering into strands and when chopped being more dispersible in aqueous media. The treated glass fibers having a coating of an aqueous treating composition, wherein the solids have a cationic surfactant having one or more primary, secondary and/or tertiary amine moieties and one or more water dispersible, poly(oxyethylene-oxyalkylene) copolymer having an oxide ratio of about 78 to about 22 to about 99 to about 1 and an average molecular weight of at least 15,000, and one or more polar functional coupling agents. Optionally, the solids may also have one or more starches that are insoluble or only incompletely soluble in cold water. Glass fibers treated with the aqueous treating compositions and produced into wet or dry chopped glass fiber strands having lengths of about 1/16 of an inch (1.58 mm) to about 3 inches (76.2 mm), have good dispersibility in aqueous media with or without addition of dispersing agents. Nonwoven, sheet-like mat is produced from aqueous dispersions having the chopped treated glass fibers, where some of the water is removed and polymeric binders, commonly referred to as wet strength binders, are applied and the mat is cured. The resulting nonwoven, sheet-like mat product has very good strength properties for use as a reinforcing element for roofing products, construction products and flooring products.

A process is provided for making an aqueous dispersible, polyurethane or poly(urethane-urea) polymer which has internal pendant, siliconate anions. The aqueous dispersion is prepared from a reaction product of polyisocyanates, organic compounds with at least 2 active hydrogens, and organosilane which is at least monofunctional in reaction with isocyanate groups on at least one organic moiety of the organo silane and also has at least one hydrolyzed or hydrolyzable groups associated with the silicone atom. Optionally, a hydrophilic additive may also be a comonomer in preparing the reaction product. The polymeric reaction product is formed at temperatures less than 200.degree. C. at atmospheric pressure. The polymeric reaction product is combined with water to form an oil-in-water dispersion and the pH of the aqueous dispersion is maintained at least about 7, when the silyl concentration on the reaction product is at least about 0.1 weight percent based on the water in the dispersion. The polymer can be a prepolymer that is chain extended in the aqueous dispersion. The aqueous dispersion can also be prepared from a prepolymer that is devoid of any organosilane used as a comonomer but where the prepolymer is dispersed and chain-extended with an organosilane that is difunctional in the isocyanate polyaddition reaction. The aqueous dispersion of the polyurethane resin is used in coating myriad substrates such as inorganic oxide substrates.

Process for producing aqueous dispersions, internally silylated and

An aqueous dispersible, isocyanate-containing polymer or prepolymer or chain extended polymer is provided which has internal pendant, reactable silane groups and which can also have internal dispersing aids. The aqueous dispersible, isocyanate-containing polymer, prepolymer, or chain extended polymer produces an aqueous dispersion of a polyurethane polymer having pendant reactable siliconate anions. The isocyanate-containing polymer is prepared from polyisocyanates, organic compounds with at least 2 active hydrogens, and organosilane which is at least monofunctional in reaction with isocyanate groups on at least one organic moiety of the organosilane. The organosilane also may have hydrolyzed or hydrolyzable groups associated with the silicone atom. The prepolymer is formed at temperatures less than 200.degree. C. at atmospheric pressure in a one shot or two step process. The polymer is combined with water to form an oil-in-water dispersion, and, if it is a prepolymer, the molecular weight is increased through chain extension. The pH of the aqueous dispersion of the polyurethane is maintained at least around 7 when the silyl concentration of the polymer is greater than 0.1 weight percent of the water in the dispersion. The aqueous dispersion can also be prepared from a prepolymer that is devoid of any organosilane used as a comonomer and where the prepolymer is dispersed and chain-extended with the difunctional organo silane. The aqueous dispersion of the polyurethane resin is used in coating myriad substrates such as inorganic oxide substrates.

Aqueous dispersion, internally silylated and dispersed polyurethane

Treated glass fibers having improved utilization of silane coupling agents are produced which have good strand handling and processing properties and which result in reinforced polymeric materials having good strength properties and good UV color stability. The treated glass fibers having an aqueous treating composition present on a substantial portion of the surface of the glass fibers, wherein the aqueous chemical treating composition has an aqueous dispersion of an internally silylated polyurethane polymer having siliconate anions and one or more dispersing agents in at least an effective dispersing amount, and water in an amount to give a total solids for the aqueous chemical composition for treatment of the glass fibers. The one or more dispersing agents, can be present as external dispersing agents in which case their amounts could be both an effective dispersing amount and an effective lubricating amount. In addition, the dispersing agents can be present with the internally silylated polyurethane polymer as an internal hydrophilic additive like nonionic and/or ionic and/or ionic precursor dispersing agents. In this case, the aqueous chemical treating composition has a glass fiber lubricant present in an effective lubricating amount. The internally silylated polyurethane may also have internal hardening segments to provide hardness to the polyurethane film formed on the glass fibers. The treated glass fibers can be used in reinforcing thermoplastic and thermosetting polymeric materials in various forms of continuous glass fibers and strand and chopped glass fibers and strands and mats of glass fibers and strands.

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Pittsburgh, PA, United States of America

Peter C Gaa