US20160297923A1 - Binder compositions and associated methods - Google Patents
Binder compositions and associated methods Download PDFInfo
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- US20160297923A1 US20160297923A1 US15/186,873 US201615186873A US2016297923A1 US 20160297923 A1 US20160297923 A1 US 20160297923A1 US 201615186873 A US201615186873 A US 201615186873A US 2016297923 A1 US2016297923 A1 US 2016297923A1
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- acid
- binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
- F16L59/028—Composition or method of fixing a thermally insulating material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249942—Fibers are aligned substantially parallel
- Y10T428/249944—Fiber is precoated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249942—Fibers are aligned substantially parallel
- Y10T428/249946—Glass fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249948—Fiber is precoated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
Definitions
- the present disclosure pertains to binder compositions for non-woven fibers.
- the present disclosure pertains to thermally-curable, polyester binders for non-woven fibers.
- Fiberglass insulation products generally include matted glass fibers that are held together by a cured thermoset polymeric resole resin.
- streams of molten glass are drawn into fibers of varying lengths and then blown into a forming chamber where they are deposited with little organization, or in varying patterns, as a mat onto a traveling conveyor.
- the fibers, while in transit in the forming chamber and while still hot from the drawing operation, are sprayed with an aqueous resin binder solution.
- the residual heat from the glass fibers and the flow of air through the fibrous mat during the forming operation will generally evaporate most of the water from the resin binder, thereby leaving the remaining components of the binder on the fibers as a viscous or semi-viscous high-solids liquid, thereby forming a “wet blanket.”
- the coated fibrous mat or wet blanket which is formed in a compressed state due to the high-velocity flow of air through the mat in the forming chamber, is then transferred out of the forming chamber to a transfer zone where the mat vertically expands due to the resiliency of the glass fibers. This vertical expansion can be important in the manufacture process of commercially acceptable fiberglass thermal or acoustical insulation products.
- the coated mat is transferred to a curing oven where heated air is blown through the mat to cure the binder and rigidly attach the glass fibers together.
- Phenol-formaldehyde (PF) resins as well as phenol-formaldehyde resins extended with urea (PFU resins), are used in conventional processes, and have been relied on heavily over the past several years to prepare binders for fiberglass insulation products. Though these resins are inexpensive and provide the cured fiberglass insulation product with the desired physical properties, they may often have high free formaldehyde content, and a distinctive or unpleasant odor limiting their use in certain applications. Further, during the manufacture of fiberglass insulation, the potential for formaldehyde emissions and worker exposure is present.
- PF and PFU resins as the main binder component for insulation products are often required to install expensive abatement equipment in order to minimize the possible exposure of workers to formaldehyde emissions and to meet certain Maximum Achieveable Control Technology (MACT) requirement standards.
- Options for formaldehyde-free products or processes include i) adding a formaldehyde scavenger to the binder to reduce or remove free formaldehyde and thereby limit its subsequent emission and/or odor; ii) allowing the resin reaction to proceed for longer periods of time to reduce the free formaldehyde present in the resin product; or iii) utilizing formaldehyde-free resin formulations.
- scavengers may lead to precipitation, resulting from the scavenger itself and/or the adduct between the scavenger and any residual formaldehyde being insoluble, thereby necessitating additional and often expensive filtration steps.
- allowing the resin reaction to proceed for an extended period of time sufficient to afford target formaldehyde levels results in a resin product having a concomitantly higher molecular weight.
- Such higher molecular weight resins may lack the desirable properties for some applications, as many tend to be sticky, causing the binder and the binder-coated fiberglass product to adhere to production equipment.
- higher molecular weight PF resins tend to have a higher “tetradimer” content.
- Tetradimer is a highly crystalline PF dimer present in phenolic resins produced under base-catalyzed conditions, which often precipitates readily. Precipitation is even more likely when free formaldehyde in the resin is scavenged. Tetradimer precipitation can result in plugged spray nozzles, and in precipitate formation in resin binder storage tanks and in the resin itself, necessitating removal.
- Suitable binder formulations advantageously have physical properties (e.g., viscosity, dilutability, and adhesiveness) and other characteristics similar to conventional PF and PFU resins, and can be made at low cost.
- Formulations that have a similar cure time and cure temperature profile, while yielding a cured fiberglass insulation product with equivalent physical properties, may allow the use of existing production equipment.
- Aqueous binder compositions are described.
- the aqueous binder composition is formaldehyde-free.
- the aqueous binder composition is thermally-curable.
- the aqueous binder composition has an alkaline pH.
- the aqueous binder composition cures to a formaldehyde-free, water-insoluble thermoset polyester resin.
- An aqueous binder composition for use in manufacturing fiber products, including non-woven fiber products such as fiber products composed of fiberglass and/or other fibers, including heat-resistant fibers and the like, is also described.
- the aqueous binder compositions and associated methods for using the binder compositions may include one or more of the features or combinations of features described herein.
- the aqueous binder composition includes a polyacid component having acid groups, or anhydride or salt derivatives thereof, and a polyhydroxy component having hydroxyl groups, where the pH of the binder composition is greater than about 7, and is illustratively in the range from about 7 to about 10.
- the composition includes a polyacid component and a polyhydroxy component where the ratio of the number of molar equivalents of acid groups, or anhydride or salt derivatives thereof, present on the polyacid component to the number of molar equivalents of hydroxyl groups present on the polyhydroxy component is in the range from about 0.6:1 to about 1.2:1.
- the composition includes a polyacid component that is a dicarboxylic acid, including, but not limited to, unsaturated aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, unsaturated cyclic dicarboxylic acids, saturated cyclic dicarboxylic acids, hydroxy-substituted derivatives thereof, and the like.
- a dicarboxylic acid including, but not limited to, unsaturated aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, unsaturated cyclic dicarboxylic acids, saturated cyclic dicarboxylic acids, hydroxy-substituted derivatives thereof, and the like.
- the composition includes a polyacid component that is a tricarboxylic acid, including, but not limited to, unsaturated aliphatic tricarboxylic acids, saturated aliphatic tricarboxylic acids, aromatic tricarboxylic acids, unsaturated cyclic tricarboxylic acids, saturated cyclic tricarboxylic acids, hydroxy-substituted derivatives thereof, and the like.
- the composition includes a polyacid component that is a tetracarboxylic, pentacarboxylic, and like polycarboxylic acids, and salts and anhydride derivatives thereof, and combinations thereof.
- the composition is an alkaline composition, where the polyacid component is neutralized by the addition of a base or where certain salts of the polyacid component are used.
- the composition includes a polyacid component, such as succinic acid, citric acid, or fumaric acid and the like that has been neutralized by the addition of a base, or is a salt.
- the polyacid component is maleic acid neutralized with, for example, aqueous ammonia.
- the polyacid component is the ammonium salt of maleate.
- the polyhydroxy component is a partially hydrolyzed polyvinyl acetate, such as, for example, an ELVANOL (available from DuPont), or a polyvinyl alcohol.
- the composition further includes a catalyst, such as an acid or an acid/salt, including inorganic and organic acids, and salts thereof.
- Illustrative organic acids include sulfonic acids and salts thereof, such as para-toluene sulfonic acid, ammonium para-toluene sulfonate, ammonium naphthalene disulfonate, and the like.
- the composition further includes a silicon-containing compound, such as silylethers and alkylsilyl ethers.
- the silicon-containing compound is an amino-substituted silicon-containing compound, including, but not limited to, gamma-aminopropyltriethoxysilane. It is appreciated that the silicon-containing compound may serve as a coupling agent during curing of the binder compositions described herein.
- a method for treating fibers, including non-woven fibers includes contacting fibers with a thermally-curable, aqueous binder composition including a polyacid component and a polyhydroxy component, as described herein, wherein the pH of the binder composition is greater than 7, or, illustratively, is in the range from about 7 to about 10, and heating the thermally-curable, aqueous binder composition at an elevated temperature that is sufficient to cure the binder composition to form a polyester.
- the polyester is substantially water-insoluble.
- the polyester is a thermoset.
- a glass fiber product in another illustrative embodiment, includes a composition obtained by heating a thermally-curable, aqueous binder composition that has been applied to fibers, such as a mat of non-woven fibers.
- the pH of the binder composition is greater than 7, or, illustratively, is in the range from about 7 to about 10.
- the binder composition includes a polyacid component and a polyhydroxy component as described herein.
- a formaldehyde-free, thermally-curable, alkaline, aqueous binder composition includes a polyacid component having acid groups, or anhydride or salt derivatives thereof, and a polyhydroxy component having hydroxyl groups, where the pH of the binder composition is greater than 7, or, illustratively, is in the range from about 7 to about 10.
- the composition may be used as a binder for non-woven fibers, such as, for example, of fiberglass in the manufacture of insulation products.
- a formaldehyde-free, alkaline, aqueous binder composition including a polyacid component and a polyhydroxy component as described herein, is left for several days at room temperature or is heated for short periods of time in the absence of a catalyst capable of accelerating or increasing the rate of chemical reaction, a water-insoluble thermoset polyester resin is produced.
- a polyacid component has been found to be capable of reacting with a polyhydroxy component, under alkaline, aqueous conditions in the absence of a catalyst, to form a polyester resin.
- the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition is substantially unreacted when it is applied to a substrate, such as a sample of non-woven fibers.
- a substrate such as a sample of non-woven fibers.
- the binder is dried and thermal curing is accomplished. It is to be understood that the drying and thermal curing may occur either sequentially, contemporaneously, or concurrently.
- thermalally-curable is intended to indicate that a structural or morphological change in the aqueous binder occurs upon heating that is sufficient to alter the properties of non-woven fibers to which an effective amount of binder has been applied; such changes include, but are not necessarily limited to, covalent reaction of components of the binder, improved adhesion of the binder components to the substrate, and hydrogen bonding of binder components.
- formaldehyde-free is meant to indicate that the aqueous binder composition is substantially free from formaldehyde, and does not liberate substantial formaldehyde as a result of drying and/or curing; typically, less than about 1 ppm formaldehyde, based on the weight of the composition, is present in a formaldehyde-free composition.
- alkaline is meant to indicate a solution pH that is greater than about 7, and is illustratively in the range from about 7 to about 10.
- aqueous includes water and mixtures composed substantially of water and other water-miscible solvents including, but not limited to, alcohols, ethers, amines, polar aprotic solvents, and the like.
- fiberglass As used herein, the terms “fiberglass,” “non-woven fiber,” and “glass fiber” are meant to indicate heat-resistant fibers suitable for withstanding elevated temperatures, such as mineral fibers, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, certain polyester fibers, rayon fibers, and glass fibers. Such fibers are substantially unaffected by exposure to temperatures above about 120° C.
- the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition includes a polyacid component having acid groups, or anhydride or salt derivative thereof.
- the polyacid component is sufficiently nonvolatile to maximize its ability to remain available for reaction with the polyhydroxy component.
- the polyacid component may be substituted with other chemical functional groups. It is appreciated that other functional groups are selected to minimize their interference with the preparation or formation of the polyester resin.
- the polyacid component may be a dicarboxylic acid, such as, for example, maleic acid.
- Suitable polyacid components include, but are not limited to, aconitic acid, adipic acid, azelaic acid, butane tetracarboxylic acid dihydride, butane tricarboxylic acid, chlorendic acid, citraconic acid, citric acid, dicyclopentadiene-maleic acid adducts, diethylenetriamine pentaacetic acid, adducts of dipentene and maleic acid, endomethylenehexachlorophthalic acid, ethylenediamine tetraacetic acid (EDTA), fully maleated rosin, maleated tall oil fatty acids, fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleated rosin-oxidize unsaturation with potassium peroxide to alcohol then carboxylic acid, malic acid, mesaconic acid, biphenol A or bisphenol F reacted via the KOLBE-Schmidt reaction with carbon dioxide to introduce 3-4 carboxyl groups
- the acid groups of the polyacid component of the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition are neutralized with a base, and thereby converted to acid salt groups, prior to their reaction with the hydroxyl groups of the polyhydroxy component to form the polyester resin.
- complete neutralization i.e., about 100% calculated on an equivalents basis, may eliminate any need to titrate or partially neutralize acid groups in the polyacid component prior to polyester formation, but it is anticipated that less-than-complete neutralization would not inhibit formation of the polyester.
- Base refers to a base which may be substantially volatile or non-volatile under conditions sufficient to promote formation of the polyester.
- the base may be a volatile base, such as, for example, aqueous ammonia; alternatively, the base may be a non-volatile base, such as, for example, sodium carbonate, and other non-volatile bases, such as sodium hydroxide, potassium hydroxide, and the like are contemplated. Neutralization may be carried out either before or after the polyacid component is mixed with the polyhydroxy component.
- the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition also includes a polyhydroxy component having hydroxyl groups.
- the polyhydroxy component is sufficiently nonvolatile to maximize its ability to remain available for reaction with the polyacid component.
- the polyhydroxy component may be a polyvinyl alcohol, a partially hydrolyzed polyvinyl acetate, or mixtures thereof.
- an 87-89% hydrolyzed polyvinyl acetate may be utilized, such as, for example, DuPont ELVANOL 51-05, which has a molecular weight of about 22,000-26,000 Da and a viscosity of 5.0-6.0 centipoises.
- ELVANOL 51-05 such as, for example, DuPont ELVANOL 51-04, ELVANOL 51-08, ELVANOL 50-14, ELVANOL 52-22, ELVANOL 50-26, and ELVANOL 50-42; and partially hydrolyzed polyvinyl acetates differing in molecular weight, viscosity, and degree of hydrolysis from ELVANOL 51-05, such as, for example, DuPont ELVANOL 51-03 (86-89% hydrolyzed), ELVANOL 70-14 (95.0-97.0% hydrolyzed), ELVANOL 70-27 (95.5-96.5% hydrolyzed), ELVANOL 60-30 (90-93% hydrolyzed), ELVANOL 70-03 (98.0-98.8% hydrolyzed), ELVANOL 51-05, such as, for example, DuPont ELVANOL 51-03 (86-89% hydrolyzed), ELVANOL 70-14 (95.0-97.0% hydrolyzed), ELVANOL 70-27 (9
- the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition may also include a catalyst capable of increasing the rate of polyester formation during curing of the binder compositions described herein.
- the catalyst may be an ammonium salt, such as, for example, ammonium para-toluene sulfonate or ammonium naphthalene disulfonate.
- catalysts include, but are not limited to, ammonium sulfate, ammonium chloride, sulfuric acid, lactic acid, lead acetate, sodium acetate, calcium acetate, zinc acetate, organotin compounds, titanium esters, antimony trioxide, germanium salts, sodium hypophosphite, sodium phosphite, methane sulfonic acid and para-toluene sulfonic acid, and mixtures thereof.
- additional catalysts may be contemplated, it is to be understood that the binder compositions described herein neither require nor are limited to any particular catalyst composition or amount thereof and the addition of such compounds is optional.
- the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition may also include a silicon-containing coupling agent (e.g., organo-silicon oil).
- a silicon-containing coupling agent e.g., organo-silicon oil
- Silicon-containing coupling agents have been marketed by the Dow-Corning Corporation, Petrarch Systems, and by the General Electric Company. Their formulation and manufacture are well known such that detailed description thereof need not be provided.
- the silicon-containing coupling agent may be compounds such as silylethers and alkylsilyl ethers.
- the silicon-containing compound is an amino-substituted silane, such as, for example, gamma-aminopropyltriethoxy silane (Dow SILQUEST A-1101).
- silicon-containing coupling agents typically are present in the binder composition in an amount within the range of about 0.1 to about 2.0 percent by weight based upon the binder solids. It is to be understood that the binder compositions described herein neither require nor are limited to any particular silicon-containing compound or amount thereof and the addition of such compounds is optional.
- the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition may be prepared by admixing a 10-50 weight percent aqueous solution of a polyacid component, already neutralized or neutralized in the presence of the polyhydroxy component, a 10-30 weight percent aqueous solution of a polyhydroxy component, and, if desired, an aqueous solution of a catalyst capable of increasing the rate of polyester formation during curing, and also, if desired, a silicon-containing coupling agent.
- binder solution compositions By varying the polyacid component, the polyhydroxy component, and optional catalyst and silicon-containing coupling agent compositions, the initial concentrations thereof, and the mixing ratio of solutions, a wide range of binder solution compositions can be prepared, wherein the pH of the binder composition is alkaline, and illustratively in the range from about 7 to about 10.
- the alkaline, formaldehyde-free binder compositions described herein provide advantages of permitting the use of existing manufacturing equipment in fiberglass manufacturing plants and eliminating the need to retrofit such plants with stainless steel equipment.
- ELVANOL 51-05 was prepared as a 14.5% solution in water (17.25 g of ELVANOL 51-05 per 119 g of solution).
- This solution exhibited a pH of 8, and consisted of approximately 24.8% ELVANOL 51-05, 32.9% maleic acid, and 42.2% sodium carbonate (as a relative percentage of total dissolved solids), and contained about 12% dissolved solids (as a percentage of total weight of solution).
- ELVANOL 51-05/maleic acid solution prepared as described in Example 2, were added 0.3 g of an 18% solution of sodium carbonate (0.05 g). The resulting mixture was stirred at room temperature to produce approximately 50.3 g of solution.
- This solution consisted of approximately 42.6% ELVANOL 51-05, 56.4% maleic acid, and 1.0% sodium carbonate (as a relative percentage of total dissolved solids), and contained about 10% dissolved solids (as a percentage of total weight of solution).
- ELVANOL 51-05/maleic acid solution prepared as described in Example 2, were added 6 g of a 19% solution of ammonia. The resulting mixture was stirred at room temperature to produce approximately 56 g of solution.
- This solution exhibited a pH of 9.5, and consisted of approximately 43.0% ELVANOL 51-05 and 57.0% maleic acid (as a relative percentage of total dissolved solids), and contained about 9% dissolved solids (as a percentage of total weight of solution).
- ELVANOL 51-05/ammonium maleate solution prepared as described in Example 5, were added 20 g of a 15% solution of ammonium para-toluene sulfonate (3 g). The resulting mixture was stirred for approximately 5 minutes at room temperature to produce approximately 70 g of clear, colorless solution.
- This solution exhibited a pH of 8.28, and consisted of approximately 26.5% ELVANOL 51-05, 35.0% maleic acid, and 38.5% ammonium para-toluene sulfonate (as a relative percentage of total dissolved solids), and contained about 11% dissolved solids (as a percentage of total weight of solution).
- ELVANOL 51-05/ammonium maleate solution prepared as described in Example 5, were added 3.3 g of a 15% solution of ammonium para-toluene sulfonate (0.5 g). The resulting mixture was stirred for approximately 9 minutes at room temperature to produce approximately 53.3 g of clear, colorless solution.
- This solution exhibited a pH of 8.17, and consisted of approximately 39.1% ELVANOL 51-05, 51.5% maleic acid, and 9.4% ammonium para-toluene sulfonate (as a relative percentage of total dissolved solids), and contained about 10% dissolved solids (as a percentage of total weight of solution).
- This solution exhibited a pH of 8.61, and consisted of approximately 50.6% ELVANOL 51-05, 35.6% maleic acid, 11.5% ammonium para-toluene sulfonate, and 2.3% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 13% dissolved solids (as a percentage of total weight of solution).
- This solution exhibited a pH of 8.60, and consisted of approximately 46.7% ELVANOL 51-05, 39.3% maleic acid, 11.7% ammonium para-toluene sulfonate, and 2.3% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 13% dissolved solids (as a percentage of total weight of solution).
- This solution exhibited a pH of 8.58, and consisted of approximately 41.4% ELVANOL 51-05, 44.2% maleic acid, 11.9% ammonium para-toluene sulfonate, and 2.4% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 12% dissolved solids (as a percentage of total weight of solution).
- This solution exhibited a pH of 8.59, and consisted of approximately 37.3% ELVANOL 51-05, 48.2% maleic acid, 12.0% ammonium para-toluene sulfonate, and 2.4% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 12% dissolved solids (as a percentage of total weight of solution).
- This solution exhibited a pH of 8.15 (at +17 hours), and consisted of approximately 38.0% ELVANOL 51-05, 50.1% maleic acid, 9.8% ammonium para-toluene sulfonate, and 2.1% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 10% dissolved solids (as a percentage of total weight of solution).
- This solution exhibited a pH of 7.91 (at +17 hours), and consisted of approximately 25.5% ELVANOL 51-05, 33.6% maleic acid, 39.5% ammonium para-toluene sulfonate, and 1.4% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 11% dissolved solids (as a percentage of total weight of solution).
- This solution exhibited a pH of 7.89 (at +17 hours), and consisted of approximately 38.0% ELVANOL 51-05, 50.2% maleic acid, 9.8% ammonium naphthalene disulfonate, and 2.0% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 10% dissolved solids (as a percentage of total weight of solution).
- This solution exhibited a pH of 8.14, and consisted of approximately 69.0% T 2894 phenol-formaldehyde resin, 23.4% urea, 5.8% ammonium para-toluene sulfonate, and 1.8% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 15% dissolved solids (as a percentage of total weight of solution).
- aqueous binder compositions In order to evaluate aqueous binder compositions under thermal curing conditions, 1-g samples of each binder composition were placed onto one or more individual aluminum plates. Each binder composition was then subjected to one or more of the following bake-out/cure conditions in pre-heated ovens in order to produce the corresponding cured binder sample: 0.5 hour at 300° F. and 0.5 hour at 350° F.
- Dry flexibility, dry strength, and wet strength were determined for cured binder samples on a scale ranging from 0, corresponding to none, to 10, corresponding to excellent, as follows: Dry flexibility was determined as the extent to which a binder sample, generally present as a film adhering to the aluminum plate, resisted breaking upon flexing the plate metal. Dry strength was determined as the extent to which a binder sample remained intact and resisted breakage following removal from a pre-heated oven. Wet strength was determined as the extent to which a binder sample appeared to have cured, as indicated by its tendency either to adhere to the surface of the aluminum plate as an intact, solid mass or, if not adherent, to remain intact and resist breakage, following addition of 10 mL of water and subsequent standing overnight at room temperature. Complete dissolution of a binder sample in 10 mL of water corresponded to a wet strength value of 0. The appearance of cured binder samples was also determined. Results are presented in Table 1.
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Abstract
Disclosed are formaldehyde-free, thermally-curable, alkaline, aqueous binder compositions, curable to formaldehyde-free, water-insoluble thermoset polyester resins, and uses thereof as binders for non-woven fibers and fiber material.
Description
- This application is a continuation of U.S. patent application Ser. No. 10/965,359, filed Oct. 13, 2004, which claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 60/552,361, filed Mar. 11, 2004, the disclosures of which are hereby incorporated herein by reference.
- The present disclosure pertains to binder compositions for non-woven fibers. In particular, the present disclosure pertains to thermally-curable, polyester binders for non-woven fibers.
- Fiberglass insulation products generally include matted glass fibers that are held together by a cured thermoset polymeric resole resin. During production of such products, streams of molten glass are drawn into fibers of varying lengths and then blown into a forming chamber where they are deposited with little organization, or in varying patterns, as a mat onto a traveling conveyor. The fibers, while in transit in the forming chamber and while still hot from the drawing operation, are sprayed with an aqueous resin binder solution. The residual heat from the glass fibers and the flow of air through the fibrous mat during the forming operation will generally evaporate most of the water from the resin binder, thereby leaving the remaining components of the binder on the fibers as a viscous or semi-viscous high-solids liquid, thereby forming a “wet blanket.” The coated fibrous mat or wet blanket, which is formed in a compressed state due to the high-velocity flow of air through the mat in the forming chamber, is then transferred out of the forming chamber to a transfer zone where the mat vertically expands due to the resiliency of the glass fibers. This vertical expansion can be important in the manufacture process of commercially acceptable fiberglass thermal or acoustical insulation products. Subsequently, the coated mat is transferred to a curing oven where heated air is blown through the mat to cure the binder and rigidly attach the glass fibers together.
- Phenol-formaldehyde (PF) resins, as well as phenol-formaldehyde resins extended with urea (PFU resins), are used in conventional processes, and have been relied on heavily over the past several years to prepare binders for fiberglass insulation products. Though these resins are inexpensive and provide the cured fiberglass insulation product with the desired physical properties, they may often have high free formaldehyde content, and a distinctive or unpleasant odor limiting their use in certain applications. Further, during the manufacture of fiberglass insulation, the potential for formaldehyde emissions and worker exposure is present. Therefore, manufacturing facilities using PF and PFU resins as the main binder component for insulation products are often required to install expensive abatement equipment in order to minimize the possible exposure of workers to formaldehyde emissions and to meet certain Maximum Achieveable Control Technology (MACT) requirement standards. Options for formaldehyde-free products or processes include i) adding a formaldehyde scavenger to the binder to reduce or remove free formaldehyde and thereby limit its subsequent emission and/or odor; ii) allowing the resin reaction to proceed for longer periods of time to reduce the free formaldehyde present in the resin product; or iii) utilizing formaldehyde-free resin formulations.
- However, the use of scavengers may lead to precipitation, resulting from the scavenger itself and/or the adduct between the scavenger and any residual formaldehyde being insoluble, thereby necessitating additional and often expensive filtration steps. Further, allowing the resin reaction to proceed for an extended period of time sufficient to afford target formaldehyde levels results in a resin product having a concomitantly higher molecular weight. Such higher molecular weight resins may lack the desirable properties for some applications, as many tend to be sticky, causing the binder and the binder-coated fiberglass product to adhere to production equipment. Furthermore, higher molecular weight PF resins tend to have a higher “tetradimer” content. Tetradimer is a highly crystalline PF dimer present in phenolic resins produced under base-catalyzed conditions, which often precipitates readily. Precipitation is even more likely when free formaldehyde in the resin is scavenged. Tetradimer precipitation can result in plugged spray nozzles, and in precipitate formation in resin binder storage tanks and in the resin itself, necessitating removal.
- Accordingly, as an alternative to PF and PFU resins, formaldehyde-free resin formulations have received increased attention for use as binders in making fiberglass insulation and other products. Suitable binder formulations advantageously have physical properties (e.g., viscosity, dilutability, and adhesiveness) and other characteristics similar to conventional PF and PFU resins, and can be made at low cost. Formulations that have a similar cure time and cure temperature profile, while yielding a cured fiberglass insulation product with equivalent physical properties, may allow the use of existing production equipment.
- Aqueous binder compositions are described. In one aspect, the aqueous binder composition is formaldehyde-free. In another aspect, the aqueous binder composition is thermally-curable. In another aspect, the aqueous binder composition has an alkaline pH. In one illustrative embodiment, the aqueous binder composition cures to a formaldehyde-free, water-insoluble thermoset polyester resin. An aqueous binder composition for use in manufacturing fiber products, including non-woven fiber products such as fiber products composed of fiberglass and/or other fibers, including heat-resistant fibers and the like, is also described. The aqueous binder compositions and associated methods for using the binder compositions may include one or more of the features or combinations of features described herein.
- In one illustrative embodiment, the aqueous binder composition includes a polyacid component having acid groups, or anhydride or salt derivatives thereof, and a polyhydroxy component having hydroxyl groups, where the pH of the binder composition is greater than about 7, and is illustratively in the range from about 7 to about 10. In another illustrative embodiment, the composition includes a polyacid component and a polyhydroxy component where the ratio of the number of molar equivalents of acid groups, or anhydride or salt derivatives thereof, present on the polyacid component to the number of molar equivalents of hydroxyl groups present on the polyhydroxy component is in the range from about 0.6:1 to about 1.2:1. In another illustrative embodiment, the composition includes a polyacid component that is a dicarboxylic acid, including, but not limited to, unsaturated aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, unsaturated cyclic dicarboxylic acids, saturated cyclic dicarboxylic acids, hydroxy-substituted derivatives thereof, and the like. In another illustrative embodiment, the composition includes a polyacid component that is a tricarboxylic acid, including, but not limited to, unsaturated aliphatic tricarboxylic acids, saturated aliphatic tricarboxylic acids, aromatic tricarboxylic acids, unsaturated cyclic tricarboxylic acids, saturated cyclic tricarboxylic acids, hydroxy-substituted derivatives thereof, and the like. In another illustrative embodiment, the composition includes a polyacid component that is a tetracarboxylic, pentacarboxylic, and like polycarboxylic acids, and salts and anhydride derivatives thereof, and combinations thereof. It is appreciated that any of these polyacids may be optionally substituted, such as with hydroxy, halo, alkyl, alkoxy, and the like. In one illustrative aspect, the composition is an alkaline composition, where the polyacid component is neutralized by the addition of a base or where certain salts of the polyacid component are used. In another illustrative embodiment, the composition includes a polyacid component, such as succinic acid, citric acid, or fumaric acid and the like that has been neutralized by the addition of a base, or is a salt. In another illustrative embodiment, the polyacid component is maleic acid neutralized with, for example, aqueous ammonia. In another illustrative embodiment, the polyacid component is the ammonium salt of maleate. In another illustrative embodiment, the polyhydroxy component is a partially hydrolyzed polyvinyl acetate, such as, for example, an ELVANOL (available from DuPont), or a polyvinyl alcohol. In another illustrative embodiment, the composition further includes a catalyst, such as an acid or an acid/salt, including inorganic and organic acids, and salts thereof. Illustrative organic acids include sulfonic acids and salts thereof, such as para-toluene sulfonic acid, ammonium para-toluene sulfonate, ammonium naphthalene disulfonate, and the like. It is appreciated that such catalysts may be capable of increasing the rate of ester formation during curing of the binder compositions described herein. In another illustrative embodiment, the composition further includes a silicon-containing compound, such as silylethers and alkylsilyl ethers. In one aspect, the silicon-containing compound is an amino-substituted silicon-containing compound, including, but not limited to, gamma-aminopropyltriethoxysilane. It is appreciated that the silicon-containing compound may serve as a coupling agent during curing of the binder compositions described herein.
- In another illustrative embodiment, a method for treating fibers, including non-woven fibers, is described. In an illustrative aspect, the method includes contacting fibers with a thermally-curable, aqueous binder composition including a polyacid component and a polyhydroxy component, as described herein, wherein the pH of the binder composition is greater than 7, or, illustratively, is in the range from about 7 to about 10, and heating the thermally-curable, aqueous binder composition at an elevated temperature that is sufficient to cure the binder composition to form a polyester. In one aspect, the polyester is substantially water-insoluble. In another aspect, the polyester is a thermoset.
- In another illustrative embodiment, a glass fiber product is described. The glass fiber product includes a composition obtained by heating a thermally-curable, aqueous binder composition that has been applied to fibers, such as a mat of non-woven fibers. In one aspect, the pH of the binder composition is greater than 7, or, illustratively, is in the range from about 7 to about 10. In one embodiment, the binder composition includes a polyacid component and a polyhydroxy component as described herein.
- In an illustrative embodiment, a formaldehyde-free, thermally-curable, alkaline, aqueous binder composition is described. The binder composition includes a polyacid component having acid groups, or anhydride or salt derivatives thereof, and a polyhydroxy component having hydroxyl groups, where the pH of the binder composition is greater than 7, or, illustratively, is in the range from about 7 to about 10. The composition may be used as a binder for non-woven fibers, such as, for example, of fiberglass in the manufacture of insulation products. In one embodiment, it has been discovered that when a formaldehyde-free, alkaline, aqueous binder composition, including a polyacid component and a polyhydroxy component as described herein, is left for several days at room temperature or is heated for short periods of time in the absence of a catalyst capable of accelerating or increasing the rate of chemical reaction, a water-insoluble thermoset polyester resin is produced. Thus, a polyacid component has been found to be capable of reacting with a polyhydroxy component, under alkaline, aqueous conditions in the absence of a catalyst, to form a polyester resin.
- In an illustrative embodiment, the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition is substantially unreacted when it is applied to a substrate, such as a sample of non-woven fibers. Upon heating, the binder is dried and thermal curing is accomplished. It is to be understood that the drying and thermal curing may occur either sequentially, contemporaneously, or concurrently. As used herein, the term “thermally-curable” is intended to indicate that a structural or morphological change in the aqueous binder occurs upon heating that is sufficient to alter the properties of non-woven fibers to which an effective amount of binder has been applied; such changes include, but are not necessarily limited to, covalent reaction of components of the binder, improved adhesion of the binder components to the substrate, and hydrogen bonding of binder components.
- The term “formaldehyde-free,” as used herein, is meant to indicate that the aqueous binder composition is substantially free from formaldehyde, and does not liberate substantial formaldehyde as a result of drying and/or curing; typically, less than about 1 ppm formaldehyde, based on the weight of the composition, is present in a formaldehyde-free composition.
- As used herein, the term “alkaline” is meant to indicate a solution pH that is greater than about 7, and is illustratively in the range from about 7 to about 10.
- As used herein, the term “aqueous” includes water and mixtures composed substantially of water and other water-miscible solvents including, but not limited to, alcohols, ethers, amines, polar aprotic solvents, and the like.
- As used herein, the terms “fiberglass,” “non-woven fiber,” and “glass fiber” are meant to indicate heat-resistant fibers suitable for withstanding elevated temperatures, such as mineral fibers, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, certain polyester fibers, rayon fibers, and glass fibers. Such fibers are substantially unaffected by exposure to temperatures above about 120° C.
- In an illustrative embodiment, the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition includes a polyacid component having acid groups, or anhydride or salt derivative thereof. In one aspect, the polyacid component is sufficiently nonvolatile to maximize its ability to remain available for reaction with the polyhydroxy component. The polyacid component may be substituted with other chemical functional groups. It is appreciated that other functional groups are selected to minimize their interference with the preparation or formation of the polyester resin. Illustratively, the polyacid component may be a dicarboxylic acid, such as, for example, maleic acid. Other suitable polyacid components are contemplated to include, but are not limited to, aconitic acid, adipic acid, azelaic acid, butane tetracarboxylic acid dihydride, butane tricarboxylic acid, chlorendic acid, citraconic acid, citric acid, dicyclopentadiene-maleic acid adducts, diethylenetriamine pentaacetic acid, adducts of dipentene and maleic acid, endomethylenehexachlorophthalic acid, ethylenediamine tetraacetic acid (EDTA), fully maleated rosin, maleated tall oil fatty acids, fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleated rosin-oxidize unsaturation with potassium peroxide to alcohol then carboxylic acid, malic acid, mesaconic acid, biphenol A or bisphenol F reacted via the KOLBE-Schmidt reaction with carbon dioxide to introduce 3-4 carboxyl groups, oxalic acid, phthalic acid, polylactic acid, sebacic acid, succinic acid, tartaric acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, trimellitic acid, and trimesic acid, and anhydrides and salts thereof, and combinations thereof.
- In an illustrative embodiment, the acid groups of the polyacid component of the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition are neutralized with a base, and thereby converted to acid salt groups, prior to their reaction with the hydroxyl groups of the polyhydroxy component to form the polyester resin. It is understood that complete neutralization, i.e., about 100% calculated on an equivalents basis, may eliminate any need to titrate or partially neutralize acid groups in the polyacid component prior to polyester formation, but it is anticipated that less-than-complete neutralization would not inhibit formation of the polyester. “Base,” as used herein, refers to a base which may be substantially volatile or non-volatile under conditions sufficient to promote formation of the polyester. Illustratively, the base may be a volatile base, such as, for example, aqueous ammonia; alternatively, the base may be a non-volatile base, such as, for example, sodium carbonate, and other non-volatile bases, such as sodium hydroxide, potassium hydroxide, and the like are contemplated. Neutralization may be carried out either before or after the polyacid component is mixed with the polyhydroxy component.
- In an illustrative embodiment, the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition also includes a polyhydroxy component having hydroxyl groups. In one aspect, the polyhydroxy component is sufficiently nonvolatile to maximize its ability to remain available for reaction with the polyacid component. The polyhydroxy component may be a polyvinyl alcohol, a partially hydrolyzed polyvinyl acetate, or mixtures thereof. Illustratively, when a partially hydrolyzed polyvinyl acetate serves as the polyhydroxy component, an 87-89% hydrolyzed polyvinyl acetate may be utilized, such as, for example, DuPont ELVANOL 51-05, which has a molecular weight of about 22,000-26,000 Da and a viscosity of 5.0-6.0 centipoises. Other partially hydrolyzed polyvinyl acetates contemplated to be useful include, but are not limited to, 87-89% hydrolyzed polyvinyl acetates differing in molecular weight and viscosity from ELVANOL 51-05, such as, for example, DuPont ELVANOL 51-04, ELVANOL 51-08, ELVANOL 50-14, ELVANOL 52-22, ELVANOL 50-26, and ELVANOL 50-42; and partially hydrolyzed polyvinyl acetates differing in molecular weight, viscosity, and degree of hydrolysis from ELVANOL 51-05, such as, for example, DuPont ELVANOL 51-03 (86-89% hydrolyzed), ELVANOL 70-14 (95.0-97.0% hydrolyzed), ELVANOL 70-27 (95.5-96.5% hydrolyzed), ELVANOL 60-30 (90-93% hydrolyzed), ELVANOL 70-03 (98.0-98.8% hydrolyzed), ELVANOL 70-04 (98.0-98.8% hydrolyzed), ELVANOL 70-06 (98.5-99.2% hydrolyzed), ELVANOL 90-50 (99.0-99.8% hydrolyzed), ELVANOL 70-20 (98.5-99.2% hydrolyzed), ELVANOL 70-30 (98.5-99.2% hydrolyzed), ELVANOL 71-30 (99.0-99.8% hydrolyzed), ELVANOL 70-62 (98.4-99.8% hydrolyzed), ELVANOL 70-63 (98.5-99.2% hydrolyzed), and ELVANOL 70-75 (98.5-99.2% hydrolyzed).
- In an illustrative embodiment, the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition may also include a catalyst capable of increasing the rate of polyester formation during curing of the binder compositions described herein. Illustratively, the catalyst may be an ammonium salt, such as, for example, ammonium para-toluene sulfonate or ammonium naphthalene disulfonate. Other suitable catalysts are contemplated to include, but are not limited to, ammonium sulfate, ammonium chloride, sulfuric acid, lactic acid, lead acetate, sodium acetate, calcium acetate, zinc acetate, organotin compounds, titanium esters, antimony trioxide, germanium salts, sodium hypophosphite, sodium phosphite, methane sulfonic acid and para-toluene sulfonic acid, and mixtures thereof. Although additional catalysts may be contemplated, it is to be understood that the binder compositions described herein neither require nor are limited to any particular catalyst composition or amount thereof and the addition of such compounds is optional.
- In an illustrative embodiment, the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition may also include a silicon-containing coupling agent (e.g., organo-silicon oil). Silicon-containing coupling agents have been marketed by the Dow-Corning Corporation, Petrarch Systems, and by the General Electric Company. Their formulation and manufacture are well known such that detailed description thereof need not be provided. Illustratively, the silicon-containing coupling agent may be compounds such as silylethers and alkylsilyl ethers. In one aspect, the silicon-containing compound is an amino-substituted silane, such as, for example, gamma-aminopropyltriethoxy silane (Dow SILQUEST A-1101). When employed in an illustrative embodiment, silicon-containing coupling agents typically are present in the binder composition in an amount within the range of about 0.1 to about 2.0 percent by weight based upon the binder solids. It is to be understood that the binder compositions described herein neither require nor are limited to any particular silicon-containing compound or amount thereof and the addition of such compounds is optional.
- In an illustrative embodiment, the formaldehyde-free, thermally-curable, alkaline, aqueous binder composition may be prepared by admixing a 10-50 weight percent aqueous solution of a polyacid component, already neutralized or neutralized in the presence of the polyhydroxy component, a 10-30 weight percent aqueous solution of a polyhydroxy component, and, if desired, an aqueous solution of a catalyst capable of increasing the rate of polyester formation during curing, and also, if desired, a silicon-containing coupling agent. By varying the polyacid component, the polyhydroxy component, and optional catalyst and silicon-containing coupling agent compositions, the initial concentrations thereof, and the mixing ratio of solutions, a wide range of binder solution compositions can be prepared, wherein the pH of the binder composition is alkaline, and illustratively in the range from about 7 to about 10. Thus, while avoiding acidic binder compositions, which tend to cause corrosion problems in manufacturing equipment, the health-related and compliance-related benefits provided by a formaldehyde-free composition are maintained. Further, the alkaline, formaldehyde-free binder compositions described herein provide advantages of permitting the use of existing manufacturing equipment in fiberglass manufacturing plants and eliminating the need to retrofit such plants with stainless steel equipment.
- The following examples illustrate embodiments of the invention in further detail. These examples are provided for illustrative purposes only and should not be construed as limiting the invention or the inventive concept to any particular physical configuration. For example, although the ratio of the number of molar equivalents of acid groups, or anhydride or salt derivatives thereof, in the polyacid component to the number of molar equivalents of hydroxyl groups in the polyhydroxy component is in the range of from about 0.6:1 to about 1.2:1, it is to be understood that, in variation of the embodiments described herein, these ratios may be altered without affecting the nature of the invention described.
- ELVANOL 51-05 was prepared as a 14.5% solution in water (17.25 g of ELVANOL 51-05 per 119 g of solution).
- To 205 g of water being stirred at room temperature were added successively 118.5 g of a 14.5% solution of ELVANOL 51-05 (17.2 g) and 76 g of a 30% solution of maleic acid (22.8 g) to produce approximately 400 g of clear, colorless solution. To 50 g of ELVANOL 51-05/maleic acid solution were added 20.3 g of an 18% solution of sodium carbonate (3.65 g). The resulting mixture was stirred at room temperature to produce approximately 70.3 g of hazy solution. This solution exhibited a pH of 8, and consisted of approximately 24.8% ELVANOL 51-05, 32.9% maleic acid, and 42.2% sodium carbonate (as a relative percentage of total dissolved solids), and contained about 12% dissolved solids (as a percentage of total weight of solution).
- To 50 g of ELVANOL 51-05/maleic acid solution, prepared as described in Example 2, were added 0.3 g of an 18% solution of sodium carbonate (0.05 g). The resulting mixture was stirred at room temperature to produce approximately 50.3 g of solution. This solution consisted of approximately 42.6% ELVANOL 51-05, 56.4% maleic acid, and 1.0% sodium carbonate (as a relative percentage of total dissolved solids), and contained about 10% dissolved solids (as a percentage of total weight of solution).
- To 50 g of ELVANOL 51-05/maleic acid solution, prepared as described in Example 2, were added 6 g of a 19% solution of ammonia. The resulting mixture was stirred at room temperature to produce approximately 56 g of solution. This solution exhibited a pH of 9.5, and consisted of approximately 43.0% ELVANOL 51-05 and 57.0% maleic acid (as a relative percentage of total dissolved solids), and contained about 9% dissolved solids (as a percentage of total weight of solution).
- To 127 g of water being stirred at room temperature were added successively 80 g of a 14.5% solution of ELVANOL 51-05 (11.6 g) and 73 g of a 27% solution of ammonium maleate (equivalent to 15.3 g of maleic acid solids) to produce approximately 280 g of clear, colorless solution. This solution exhibited a pH of 7.94 (after 9 days), and consisted of approximately 43% ELVANOL 51-05 and 57% maleic acid (as a relative percentage of total dissolved solids), and contained about 10% dissolved solids (as a percentage of total weight of solution). Upon standing for eleven days at room temperature, a tough, insoluble film was observed on the bottom of the reaction flask.
- To 50 g of ELVANOL 51-05/ammonium maleate solution, prepared as described in Example 5, were added 20 g of a 15% solution of ammonium para-toluene sulfonate (3 g). The resulting mixture was stirred for approximately 5 minutes at room temperature to produce approximately 70 g of clear, colorless solution. This solution exhibited a pH of 8.28, and consisted of approximately 26.5% ELVANOL 51-05, 35.0% maleic acid, and 38.5% ammonium para-toluene sulfonate (as a relative percentage of total dissolved solids), and contained about 11% dissolved solids (as a percentage of total weight of solution).
- To 50 g of ELVANOL 51-05/ammonium maleate solution, prepared as described in Example 5, were added 3.3 g of a 15% solution of ammonium para-toluene sulfonate (0.5 g). The resulting mixture was stirred for approximately 9 minutes at room temperature to produce approximately 53.3 g of clear, colorless solution. This solution exhibited a pH of 8.17, and consisted of approximately 39.1% ELVANOL 51-05, 51.5% maleic acid, and 9.4% ammonium para-toluene sulfonate (as a relative percentage of total dissolved solids), and contained about 10% dissolved solids (as a percentage of total weight of solution).
- To 148 g of water being stirred at room temperature were added successively 303 g of a 14.5% solution of ELVANOL 51-05 (43.9 g), 147 g of a 27% solution of ammonium maleate (equivalent to 30.9 g of maleic acid solids), 67 g of a 15% solution of ammonium para-toluene sulfonate (10.0 g), and 2.0 g of SILQUEST A-1101 silane to produce approximately 667 g of solution. This solution exhibited a pH of 8.61, and consisted of approximately 50.6% ELVANOL 51-05, 35.6% maleic acid, 11.5% ammonium para-toluene sulfonate, and 2.3% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 13% dissolved solids (as a percentage of total weight of solution).
- To 162 g of water being stirred at room temperature were added successively 276 g of a 14.5% solution of ELVANOL 51-05 (40.0 g), 160 g of a 27% solution of ammonium maleate (equivalent to 33.6 g of maleic acid solids), 67 g of a 15% solution of ammonium para-toluene sulfonate (10.0 g), and 2.0 g of SILQUEST A-1101 silane to produce approximately 667 g of solution. This solution exhibited a pH of 8.60, and consisted of approximately 46.7% ELVANOL 51-05, 39.3% maleic acid, 11.7% ammonium para-toluene sulfonate, and 2.3% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 13% dissolved solids (as a percentage of total weight of solution).
- To 54 g of water being stirred at room temperature were added successively 72 g of a 14.5% solution of ELVANOL 51-05 (10.4 g), 53 g of a 27% solution of ammonium maleate (equivalent to 11.1 g of maleic acid solids), 20 g of a 15% solution of ammonium para-toluene sulfonate (3 g), and 0.6 g of SILQUEST A-1101 silane to produce approximately 200 g of solution. This solution exhibited a pH of 8.58, and consisted of approximately 41.4% ELVANOL 51-05, 44.2% maleic acid, 11.9% ammonium para-toluene sulfonate, and 2.4% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 12% dissolved solids (as a percentage of total weight of solution).
- To 58 g of water being stirred at room temperature were added successively 64 g of a 14.5% solution of ELVANOL 51-05 (9.3 g), 57 g of a 27% solution of ammonium maleate (equivalent to 12.0 g of maleic acid solids), 20 g of a 15% solution of ammonium para-toluene sulfonate (3 g), and 0.6 g of SILQUEST A-1101 silane to produce approximately 200 g of solution. This solution exhibited a pH of 8.59, and consisted of approximately 37.3% ELVANOL 51-05, 48.2% maleic acid, 12.0% ammonium para-toluene sulfonate, and 2.4% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 12% dissolved solids (as a percentage of total weight of solution).
- To 126 g of water being stirred at room temperature were added successively 80 g of a 14.5% solution of ELVANOL 51-05 (11.6 g), 20 g of a 15% solution of ammonium para-toluene sulfonate (3 g), 73 g of a 27% solution of ammonium maleate (equivalent to 15.3 g of maleic acid solids), and 0.65 g of SILQUEST A-1101 silane to produce approximately 300 g of clear, colorless solution. This solution exhibited a pH of 8.15 (at +17 hours), and consisted of approximately 38.0% ELVANOL 51-05, 50.1% maleic acid, 9.8% ammonium para-toluene sulfonate, and 2.1% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 10% dissolved solids (as a percentage of total weight of solution).
- To 126 g of water being stirred at room temperature were added successively 80 g of a 14.5% solution of ELVANOL 51-05 (11.6 g), 73 g of a 27% solution of ammonium maleate (equivalent to 15.3 g of maleic acid solids), 120 g of a 15% solution of ammonium para-toluene sulfonate (18 g), and 0.63 g of SILQUEST A-1101 silane to produce approximately 400 g of clear, colorless solution. This solution exhibited a pH of 7.91 (at +17 hours), and consisted of approximately 25.5% ELVANOL 51-05, 33.6% maleic acid, 39.5% ammonium para-toluene sulfonate, and 1.4% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 11% dissolved solids (as a percentage of total weight of solution).
- To 126 g of water being stirred at room temperature were added successively 80 g of a 14.5% solution of ELVANOL 51-05 (11.6 g), 73 g of a 27% solution of ammonium maleate (equivalent to 15.3 g of maleic acid solids), 10 g of a 30% solution of ammonium naphthalene disulfonate (3 g), and 0.6 g of SILQUEST A-1101 silane to produce approximately 290 g of clear, colorless solution. This solution exhibited a pH of 7.89 (at +17 hours), and consisted of approximately 38.0% ELVANOL 51-05, 50.2% maleic acid, 9.8% ammonium naphthalene disulfonate, and 2.0% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 10% dissolved solids (as a percentage of total weight of solution).
- To 81 g of a 51% solution of T 2894 phenol-formaldehyde resin (41.3 g) were added 35 g of a 40% solution of urea (14 g). The resulting solution was stirred at room temperature and then were added successively 251 g of water, 7.9 g of a 19% solution of ammonia, 23.3 g of a 15% solution of ammonium para-toluene sulfonate (3.5 g), and 1.05 g of SILQUEST A-1101 silane to produce approximately 400 g of clear, colorless solution. This solution exhibited a pH of 8.14, and consisted of approximately 69.0% T 2894 phenol-formaldehyde resin, 23.4% urea, 5.8% ammonium para-toluene sulfonate, and 1.8% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 15% dissolved solids (as a percentage of total weight of solution).
- To 112.98 g of a 25.3% solution of Rohm-Haas T SET #1 (28.6 g) were added 77.58 g of water to produce approximately 190.56 g of clear, colorless solution. This solution, consisting of 100% T SET #1 (as a relative percentage of total dissolved solids), exhibited a pH of 4.08 and contained about 15% dissolved solids (as a percentage of total weight of solution).
- To 99.75 g of Rohm-Haas T SET #1 solution, prepared as described in Example 16, were added 0.23 g of SILQUEST A-1101 silane to produce approximately 100 g of clear, colorless solution. This solution exhibited a pH of 4.06, and consisted of approximately 98.5% T SET #1 and 1.5% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained about 15% dissolved solids (as a percentage of total weight of solution).
- In order to evaluate aqueous binder compositions under thermal curing conditions, 1-g samples of each binder composition were placed onto one or more individual aluminum plates. Each binder composition was then subjected to one or more of the following bake-out/cure conditions in pre-heated ovens in order to produce the corresponding cured binder sample: 0.5 hour at 300° F. and 0.5 hour at 350° F.
- Dry flexibility, dry strength, and wet strength were determined for cured binder samples on a scale ranging from 0, corresponding to none, to 10, corresponding to excellent, as follows: Dry flexibility was determined as the extent to which a binder sample, generally present as a film adhering to the aluminum plate, resisted breaking upon flexing the plate metal. Dry strength was determined as the extent to which a binder sample remained intact and resisted breakage following removal from a pre-heated oven. Wet strength was determined as the extent to which a binder sample appeared to have cured, as indicated by its tendency either to adhere to the surface of the aluminum plate as an intact, solid mass or, if not adherent, to remain intact and resist breakage, following addition of 10 mL of water and subsequent standing overnight at room temperature. Complete dissolution of a binder sample in 10 mL of water corresponded to a wet strength value of 0. The appearance of cured binder samples was also determined. Results are presented in Table 1.
-
TABLE 1 Testing Results from Cured Binder Samples Example No. Cure Dry Dry Wet COOH/OH (composition as % solids) Temp Flexibility Strength Strength Ratio Appearance 1 PVA (100%) 300° F. — — 0 — Film 2 300° F. — — 0 1.25 Opaque PVA/MA/SC (24.8%:32.9%:42.2%) 3 300° F. — — 5 1.25 Transparent PVA/MA/SC (42.6%:56.4%:1.0%) 4 300° F. — — 3 1.25 Opaque PVA/MA-NH3 (43%:57%) 5 300° F. — — 0 1.25 Off-white PVA/AM (43%:57%) 350° F. — — 5 Orange-yellow 6 350° F. — 10 5 1.24 Dirty-orange PVA/AM/ATS (26.5%:35.0%:38.5%) 7 350° F. — 10 5 1.24 Yellow-orange PVA/AM/ATS (39.1%:51.5%:9.4%) 8 300° F. 10 — 0 Colorless PVA/AM/ATS/SILQUEST 350° F. 0 — 8 0.66 Orange-brown (50.6%:35.6%:11.5%:2.3%) 9 300° F. 10 — 5 Colorless PVA/AM/ATS/SILQUEST 350° F. 0 — 8 0.79 Light orange (46.7%:39.3%:11.7%:2.3%) 10 300° F. 10 — 6 Light tan PVA/AM/ATS/SILQUEST 350° F. 10 — 9 1.00 — (41.4%:44.2%:11.9%:2.4%) 11 300° F. “tacky” — 1 Colorless PVA/AM/ATS/SILQUEST 350° F. — — 9 1.22 Light orange (37.3%:48.2%:12.0%:2.4%) 12 300° F. 10 10 2 Off-white PVA/AM/ATS/SILQUEST 350° F. 10 10 8 1.24 Orange-brown (38.0%:50.1%:9.8%:2.1%) 13 300° F. 10 10 2 Off-white PVA/AM/ATS/SILQUEST 350° F. 0 10 5 1.24 Brown-orange (25.5%:33.6%:39.5%:1.4%) 14 300° F. 10 10 0 White PVA/AM/AND/SILQUEST 350° F. 10 10 4 1.24 Light brown (38.0%:50.2%:9.8%:2.0%) 15 300° F. 0 10 10 Yellow PF/U/ATS/SILQUEST 350° F. 0 10 10 — Dull yellow (69.0%:23.4%:5.8%:1.8%) 16 300° F. 10 10 8 Colorless T SET #1 (100%) 350° F. 0 10 8 — Colorless 17 300° F. 10 10 8 Colorless T SET #1-SILQUEST 350° F. 0 10 8 — — (98.5%:1.5%) PVA = ELVANOL 51-05 (87-89% hydrolyzed polyvinyl acetate) ATS = Ammonium para-toluene sulfonate SC = Sodium Carbonate SILQUEST = Gamma-aminopropyltriethoxy (A-1101) silane AND = Ammonium naphthalene disulfonate U = Urea MA = Maleic acid AS = Ammonium sulfate NH3 = Aqueous ammonia AM = Ammonium maleate PF = Phenol formaldehyde resin T-Set #1 = Rohm-Haas formaldehyde-free binder - While certain embodiments of the present invention have been described and/or exemplified above, it is contemplated that considerable variation and modification thereof are possible. Accordingly, the present invention is not limited to the particular embodiments described and/or exemplified herein.
Claims (21)
1. A binder comprising
a polyester polymer, the polyester polymer comprising a reaction product of a polycarboxylic acid component and a polymeric polyhydroxyl component in the presence of a catalyst, wherein a solution of the polycarboxylic acid component, the polymeric polyhydroxyl component, and the catalyst has an alkaline pH and the polycarboxylic acid component is a dicarboxylic acid, tricarboxylic acid, tetra-carboxylic acid, or penta-carboxylic acid, or salts or anhydride derivatives thereof, or combinations thereof.
2. The binder of claim 1 , wherein the alkaline pH is in the range from about 7 to about 10.
3. The binder of claim 1 , wherein the solution has the alkaline pH due to inclusion of a base in the solution.
4. The binder of claim 3 , wherein the base is sodium hydroxide.
5. The binder of claim 4 , wherein the polyester polymer is colorless.
6. The binder of claim 3 , wherein the base is ammonium hydroxide.
7. The binder of claim 4 , wherein the polyester polymer is light tan.
8. The binder of claim 1 , wherein the polycarboxylic acid component is citric acid.
9. The binder of claim 1 , wherein the catalyst is sodium hypophosphite.
10. A method of making a formaldehyde-free binder comprising
drying an aqueous solution comprising (a) a polycarboxylic acid component selected from a group consisting of a dicarboxylic acid, tricarboxylic acid, tetra carboxylic acid, penta carboxylic acid, and anhydride derivatives thereof, (b) a polymeric polyhydroxyl component, (c) a catalyst, and (d) a base to form a dried mixture,
curing the dried mixture to form the formaldehyde-free binder.
11. The method of claim 10 , wherein the aqueous solution includes sufficient base to have an alkaline pH.
12. The method of claim 10 , wherein the aqueous solution further comprises a silicon-containing compound.
13. The method of claim 12 , wherein the silicon-containing compound is a silylethers or an alkylsilyl ethers.
14. The method of claim 12 , wherein the silicon-containing compound is gamma-aminopropyltriethoxy silane.
15. The method of claim 10 , wherein the polycarboxylic acid component is citric acid.
16. The method of claim 10 , wherein the catalyst is selected from the group consisting of ammonium para-toluene sulfonate, ammonium naphthalene disulfonate, ammonium sulfate, ammonium chloride, sulfuric acid, lactic acid, lead acetate, sodium acetate, calcium acetate, zinc acetate, organotin compounds, titanium esters, antimony trioxide, germanium salts, sodium hypophosphite, sodium phosphite, methane sulfonic acid and para-toluene sulfonic acid, and mixtures thereof.
17. The method of claim 10 , wherein the catalyst is sodium hypophosphite.
18. The method of claim 10 , wherein the base is selected from the group consisting ammonia, sodium carbonate, sodium hydroxide, and potassium hydroxide.
19. The method of claim 10 , wherein the base is selected from the group consisting ammonia, sodium carbonate, sodium hydroxide, and potassium hydroxide.
20. An insulation product comprising
a formaldehyde-free polymeric binder composition in contact with mineral fibers, the formaldehyde-free polymeric binder comprising a product of a dried and cured alkaline aqueous solution, the solution comprising a polymeric polyhydroxyl component, a polycarboxylic acid component selected from a dicarboxylic acid, tricarboxylic acid, tetra-carboxylic acid, or penta-carboxylic acid, and a catalyst.
21.-25. (canceled)
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Families Citing this family (59)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7842382B2 (en) | 2004-03-11 | 2010-11-30 | Knauf Insulation Gmbh | Binder compositions and associated methods |
JP2008516071A (en) * | 2004-10-13 | 2008-05-15 | クナーフ インシュレーション ゲーエムベーハー | Polyester binding composition |
CN100513344C (en) * | 2005-01-31 | 2009-07-15 | 花王株式会社 | Process for producing a naphthalenesulfonate formaldehyde condensate |
KR20220062129A (en) | 2005-07-26 | 2022-05-13 | 크나우프 인설레이션, 인크. | Binders and materials made therewith |
EP1897862A1 (en) * | 2006-09-05 | 2008-03-12 | Rockwool International A/S | Mineral wool composite moldings |
EP1935906B1 (en) * | 2006-12-22 | 2011-02-23 | Rohm and Haas Company | Curable aqueous composition |
EP1942119A1 (en) * | 2006-12-22 | 2008-07-09 | Rohm and Haas France SAS | Curable aqueous composition |
BRPI0721232B1 (en) | 2007-01-25 | 2023-01-24 | Knauf Insulation Limited | COMPOSITE WOOD PLATE |
CN101668713B (en) | 2007-01-25 | 2012-11-07 | 可耐福保温材料有限公司 | Mineral fibre board |
US9828287B2 (en) | 2007-01-25 | 2017-11-28 | Knauf Insulation, Inc. | Binders and materials made therewith |
EP2137223B1 (en) * | 2007-04-13 | 2019-02-27 | Knauf Insulation GmbH | Composite maillard-resole binders |
CN101802031B (en) * | 2007-07-05 | 2012-10-17 | 可耐福保温材料有限公司 | Hydroxymonocarboxylic acid-based maillard binder |
GB0715100D0 (en) | 2007-08-03 | 2007-09-12 | Knauf Insulation Ltd | Binders |
WO2009080696A2 (en) * | 2007-12-21 | 2009-07-02 | Akzo Nobel N.V. | Thermosetting polysaccharides |
CA2709888A1 (en) * | 2007-12-21 | 2009-07-02 | Akzo Nobel N.V. | Thermosetting polymers |
EP2085365A1 (en) | 2008-02-01 | 2009-08-05 | Rockwool International A/S | Method of producing a bonded mineral fibre product |
US8580139B2 (en) * | 2008-08-02 | 2013-11-12 | Georgia-Pacific Chemicals Llc | Dedusting compositions and methods for making and using same |
CN102112574B (en) * | 2008-08-02 | 2014-07-02 | 佐治亚-太平洋化工品有限公司 | Pitch emulsions |
JP5255411B2 (en) * | 2008-11-27 | 2013-08-07 | 昭和電工株式会社 | Thermally crosslinkable polymer aqueous emulsion composition, method for producing the same, and fiber treating agent |
WO2010120748A1 (en) * | 2009-04-13 | 2010-10-21 | Owens Corning Intellectual Capital, Llc | Soft fiber insulation product |
US20110003522A1 (en) * | 2009-05-15 | 2011-01-06 | Liang Chen | Bio-based aqueous binder for fiberglass insulation materials and non-woven mats |
US9718729B2 (en) * | 2009-05-15 | 2017-08-01 | Owens Corning Intellectual Capital, Llc | Biocides for bio-based binders, fibrous insulation products and wash water systems |
US20110021101A1 (en) * | 2009-06-29 | 2011-01-27 | Hawkins Christopher M | Modified starch based binder |
CA2770396A1 (en) | 2009-08-07 | 2011-02-10 | Knauf Insulation | Molasses binder |
WO2011028964A1 (en) * | 2009-09-02 | 2011-03-10 | Georgia-Pacific Chemicals Llc | Dedusting agents for fiberglass products and methods for making and using same |
US20110223364A1 (en) | 2009-10-09 | 2011-09-15 | Hawkins Christopher M | Insulative products having bio-based binders |
WO2011044490A1 (en) | 2009-10-09 | 2011-04-14 | Owens Corning Intellectual Capital, Llc | Bio-based binders for insulation and non-woven mats |
EP2566903B1 (en) | 2010-05-07 | 2021-07-14 | Knauf Insulation | Carbohydrate binders and materials made therewith |
AU2011249759B2 (en) | 2010-05-07 | 2014-11-06 | Knauf Insulation | Carbohydrate polyamine binders and materials made therewith |
EP2576882B1 (en) | 2010-06-07 | 2015-02-25 | Knauf Insulation | Fiber products having temperature control additives |
EP2617088B2 (en) * | 2010-09-17 | 2020-12-02 | Knauf Insulation GmbH | Organic acid carbohydrate binders and materials made therewith |
US20130211068A1 (en) * | 2010-10-08 | 2013-08-15 | Kevin R. Anderson | Binder, composition for use in making the binder, and methods of making the same |
US10017648B2 (en) * | 2010-12-16 | 2018-07-10 | Awi Licensing Llc | Sag resistant, formaldehyde-free coated fibrous substrate |
WO2012138723A1 (en) | 2011-04-07 | 2012-10-11 | Cargill, Incorporated | Bio-based binders including carbohydrates and a pre-reacted product of an alcohol or polyol and a monomeric or polymeric polycarboxylic acid |
CA2834816C (en) | 2011-05-07 | 2020-05-12 | Knauf Insulation | Liquid high solids binder composition |
US9957409B2 (en) | 2011-07-21 | 2018-05-01 | Owens Corning Intellectual Capital, Llc | Binder compositions with polyvalent phosphorus crosslinking agents |
GB201115172D0 (en) | 2011-09-02 | 2011-10-19 | Knauf Insulation Ltd | Carbohydrate based binder system and method of its production |
GB201206193D0 (en) | 2012-04-05 | 2012-05-23 | Knauf Insulation Ltd | Binders and associated products |
EP2838703B1 (en) | 2012-04-18 | 2019-06-12 | Knauf Insulation GmbH | Molding process |
GB201214734D0 (en) | 2012-08-17 | 2012-10-03 | Knauf Insulation Ltd | Wood board and process for its production |
CA2892900C (en) | 2012-12-05 | 2020-08-11 | Benedicte Pacorel | Method for manufacturing an article comprising a collection of matter bound by a cured binder |
JP5426787B2 (en) * | 2013-01-29 | 2014-02-26 | 昭和電工株式会社 | Method for producing heat-crosslinking polymer aqueous emulsion composition, method for producing treated paper, and method for producing treated fiber |
WO2014165176A2 (en) | 2013-03-13 | 2014-10-09 | Knauf Insulation Gmbh | Molding process for insulation product |
US11401204B2 (en) | 2014-02-07 | 2022-08-02 | Knauf Insulation, Inc. | Uncured articles with improved shelf-life |
GB201408909D0 (en) | 2014-05-20 | 2014-07-02 | Knauf Insulation Ltd | Binders |
JP6557464B2 (en) * | 2014-12-10 | 2019-08-07 | パラマウント硝子工業株式会社 | Insulating fiber-absorbing sound absorbing material having flexibility and method for producing the same |
GB201517867D0 (en) | 2015-10-09 | 2015-11-25 | Knauf Insulation Ltd | Wood particle boards |
DK3464698T3 (en) * | 2016-06-06 | 2022-07-25 | Owens Corning Intellectual Capital Llc | Binder system |
GB201610063D0 (en) | 2016-06-09 | 2016-07-27 | Knauf Insulation Ltd | Binders |
GB201701569D0 (en) | 2017-01-31 | 2017-03-15 | Knauf Insulation Ltd | Improved binder compositions and uses thereof |
EP3695040B1 (en) | 2017-10-09 | 2024-03-20 | Owens Corning Intellectual Capital, LLC | Aqueous binder compositions |
JP7219271B2 (en) | 2017-10-09 | 2023-02-07 | オウェンス コーニング インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | Aqueous binder composition |
GB201804908D0 (en) | 2018-03-27 | 2018-05-09 | Knauf Insulation Ltd | Binder compositions and uses thereof |
GB201804907D0 (en) | 2018-03-27 | 2018-05-09 | Knauf Insulation Ltd | Composite products |
US10927246B2 (en) * | 2018-09-14 | 2021-02-23 | Knauf Insulation, Inc. | Benzoic sulfimide binders and insulation articles comprising the same |
US11813833B2 (en) | 2019-12-09 | 2023-11-14 | Owens Corning Intellectual Capital, Llc | Fiberglass insulation product |
EP4019479A1 (en) | 2020-12-23 | 2022-06-29 | Prefere Resins Holding GmbH | Water-dilutable binders |
EP4206374A1 (en) * | 2021-12-31 | 2023-07-05 | Arkema France | Chemically bonded nonwoven substrates |
WO2024121397A1 (en) | 2022-12-09 | 2024-06-13 | Knauf Insulation | Mineral fibre products |
Family Cites Families (217)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US38017A (en) * | 1863-03-24 | Improvement in treating gas for illumination | ||
US77055A (en) * | 1868-04-21 | Improved boot-heel | ||
US135433A (en) * | 1873-02-04 | Improvement in boxes for preserving cake and bread | ||
US161108A (en) * | 1875-03-23 | Improvement in smoke-stack heater-pipes | ||
US19168A (en) * | 1858-01-19 | Sceoll-sawiktg machine | ||
US98947A (en) * | 1870-01-18 | Improvement in horse-power | ||
US32253A (en) * | 1861-05-07 | Pttefls | ||
US111480A (en) * | 1871-01-31 | Improvement in concrete blocks for paving | ||
US215153A (en) * | 1879-05-06 | Improvement in nail-feeding machines | ||
US252855A (en) * | 1882-01-24 | William p | ||
US6390A (en) * | 1849-04-24 | Frame for mosquito-bars | ||
US91185A (en) * | 1869-06-08 | Improvement in sawing-machine | ||
US254285A (en) * | 1882-02-28 | David w | ||
US9582A (en) * | 1853-02-15 | wells | ||
US152824A (en) * | 1874-07-07 | Improvement in bosom-boards | ||
US175826A (en) * | 1876-04-11 | d dedreux | ||
US198954A (en) * | 1878-01-08 | Improvement in | ||
US275133A (en) * | 1883-04-03 | Two-wheeled vehicle | ||
US99870A (en) * | 1870-02-15 | Improved hand clothes-washer | ||
US1886353A (en) | 1922-04-27 | 1932-11-01 | John Stogdell Stokes | Synthetic resin and method of making same |
US1801052A (en) | 1923-02-06 | 1931-04-14 | Meigsoid Corp | Resinous condensation product and process of making same |
US1801053A (en) | 1925-01-22 | 1931-04-14 | Meigsoid Corp | Carbohydrate product and process of making same |
US2215825A (en) | 1938-03-16 | 1940-09-24 | Matilda Wallace | Core binder |
US2371990A (en) * | 1942-02-18 | 1945-03-20 | Du Pont | Polymeric esters |
BE471265A (en) | 1942-04-02 | |||
US3232821A (en) | 1964-12-11 | 1966-02-01 | Ferro Corp | Felted fibrous mat and apparatus for manufacturing same |
US3297419A (en) | 1965-08-17 | 1967-01-10 | Fyr Tech Products Inc | Synthetic fuel log and method of manufacture |
US3856606A (en) | 1968-06-17 | 1974-12-24 | Union Carbide Corp | Coupling solid substrates using silyl peroxide compounds |
SU374400A1 (en) | 1970-07-09 | 1973-03-20 | METHOD OF OBTAINING NONWAVE MATERIALS | |
US3867119A (en) | 1970-07-20 | 1975-02-18 | Paramount Glass Mfg Co Ltd | Apparatus for manufacturing glass fibers |
US3826767A (en) | 1972-01-26 | 1974-07-30 | Calgon Corp | Anionic dextran graft copolymers |
US3791807A (en) | 1972-05-02 | 1974-02-12 | Certain Teed Prod Corp | Waste water reclamation in fiber glass operation |
IT971367B (en) | 1972-11-30 | 1974-04-30 | Sir Soc Italiana Resine Spa | PROCEDURE FOR THE CONTINUOUS PREPARATION OF UNSATURATED POLYESTERS |
US3802897A (en) | 1973-02-23 | 1974-04-09 | Anheuser Busch | Water resistant starch adhesive |
US3809664A (en) | 1973-08-16 | 1974-05-07 | Us Agriculture | Method of preparing starch graft polymers |
US4054713A (en) | 1973-12-28 | 1977-10-18 | Kao Soap Co., Ltd. | Process for preparing glass fiber mats |
US4107379A (en) | 1974-02-22 | 1978-08-15 | John Stofko | Bonding of solid lignocellulosic material |
US4183997A (en) | 1974-02-22 | 1980-01-15 | John Jansky | Bonding of solid lignocellulosic material |
US4014726A (en) | 1974-03-18 | 1977-03-29 | Owens-Corning Fiberglas Corporation | Production of glass fiber products |
US4028290A (en) | 1975-10-23 | 1977-06-07 | Hercules Incorporated | Highly absorbent modified polysaccharides |
US4048127A (en) | 1976-07-22 | 1977-09-13 | Cpc International Inc. | Carbohydrate-based condensation resin |
US4148765A (en) | 1977-01-10 | 1979-04-10 | The Dow Chemical Company | Polyester resins containing dicyclopentadiene |
US4097427A (en) | 1977-02-14 | 1978-06-27 | Nalco Chemical Company | Cationization of starch utilizing alkali metal hydroxide, cationic water-soluble polymer and oxidant for improved wet end strength |
DE2721186C2 (en) | 1977-05-11 | 1986-04-24 | Bayer Ag, 5090 Leverkusen | Process for the preparation of a mixture of low molecular weight polyhydroxyl compounds |
DE2833138A1 (en) | 1978-07-28 | 1980-02-07 | Bayer Ag | METHYLOLATED MONO AND OLIGOSACCHARIDES |
JPS5811193Y2 (en) | 1978-09-25 | 1983-03-02 | 欣一 橋詰 | Korean ginseng smoking pipe |
US4233432A (en) | 1979-05-10 | 1980-11-11 | United States Steel Corporation | Dicyclopentadiene polyester resins |
US4296173A (en) | 1979-09-13 | 1981-10-20 | Ppg Industries, Inc. | Glass fibers with reduced tendency to form gumming deposits and sizing composition comprising two starches with different amylose content |
US4246367A (en) | 1979-09-24 | 1981-01-20 | United States Steel Corporation | Dicyclopentadiene polyester resins |
US4278573A (en) | 1980-04-07 | 1981-07-14 | National Starch And Chemical Corporation | Preparation of cationic starch graft copolymers from starch, N,N-methylenebisacrylamide, and polyamines |
US4330443A (en) | 1980-06-18 | 1982-05-18 | The United States Of America As Represented By The Secretary Of Agriculture | Dry chemical process for grafting acrylic and methyl acrylic ester and amide monomers onto starch-containing materials |
GB2079801B (en) | 1980-06-27 | 1984-03-14 | Tba Industrial Products Ltd | Weld splash resistant glass fibre fabrics |
GB2078805A (en) | 1980-06-27 | 1982-01-13 | Tba Industrial Products Ltd | Fire and Weld Splash Resistant for Glass Fabric |
US4400496A (en) | 1980-09-22 | 1983-08-23 | University Of Florida | Water-soluble graft copolymers of starch-acrylamide and uses therefor |
JPS57101100U (en) | 1980-12-12 | 1982-06-22 | ||
US4357194A (en) | 1981-04-14 | 1982-11-02 | John Stofko | Steam bonding of solid lignocellulosic material |
JPS5811193A (en) * | 1981-07-11 | 1983-01-21 | Ricoh Co Ltd | Thermo-sensitive recording material |
US4464523A (en) | 1983-05-16 | 1984-08-07 | National Starch And Chemical Corporation | Process for the preparation of graft copolymers of cellulose derivatives and diallyl, dialkyl ammonium halides |
US4668716A (en) | 1983-09-30 | 1987-05-26 | Union Carbide Corporation | Novel fatty ethenoid acylaminoorganosilicon compounds and their use as a coupling agent |
US4524164A (en) | 1983-12-02 | 1985-06-18 | Chemical Process Corporation | Thermosetting adhesive resins |
US4754056A (en) | 1985-04-05 | 1988-06-28 | Desoto, Inc. | Radiation-curable coatings containing reactive pigment dispersants |
SE8504501D0 (en) | 1985-09-30 | 1985-09-30 | Astra Meditec Ab | METHOD OF FORMING AN IMPROVED HYDROPHILIC COATING ON A POLYMER SURFACE |
US4692478A (en) | 1986-03-14 | 1987-09-08 | Chemical Process Corporation | Process for preparation of resin and resin obtained |
DE3629470A1 (en) | 1986-08-29 | 1988-03-10 | Basf Lacke & Farben | CARBOXYL GROUPS AND TERTIAL AMINO GROUPS CONTAINING POLYCONDENSATION AND / OR ADDITION PRODUCT, COATING AGENTS BASED ON THE SAME AND THEIR USE |
IL80298A (en) | 1986-10-14 | 1993-01-31 | Res & Dev Co Ltd | Eye drops |
GB8809486D0 (en) | 1987-04-22 | 1988-05-25 | Micropore International Ltd | Procedure to manufacture thermal insulating material for use at high temperatures |
US4845162A (en) | 1987-06-01 | 1989-07-04 | Allied-Signal Inc. | Curable phenolic and polyamide blends |
JP2628697B2 (en) * | 1987-07-10 | 1997-07-09 | フィリップス エレクトロニクス ネムローゼ フェンノートシャップ | Linear integrated resistor |
DE3734752A1 (en) | 1987-10-14 | 1989-05-03 | Basf Ag | METHOD FOR THE PRODUCTION OF AQUEOUS (METH) ACRYLIC ACID ESTER COPOLYMER DISPERSIONS IN TWO STAGES AND THE USE THEREOF AS IMPREGNANT, COATING AND BINDING AGENT FOR FLAT FIBER FABRICS |
SE464687B (en) | 1987-11-10 | 1991-06-03 | Biocarb Ab | PROCEDURES FOR PREPARING A GEL PRODUCT |
US5095054A (en) | 1988-02-03 | 1992-03-10 | Warner-Lambert Company | Polymer compositions containing destructurized starch |
US5441713A (en) | 1988-04-29 | 1995-08-15 | Nalco Fuel Tech | Hardness suppression in urea solutions |
US5582682A (en) | 1988-12-28 | 1996-12-10 | Ferretti; Arthur | Process and a composition for making cellulosic composites |
US5371194A (en) | 1988-12-28 | 1994-12-06 | Ferretti; Arthur | Biomass derived thermosetting resin |
US5278222A (en) | 1989-02-13 | 1994-01-11 | Rohm And Haas Company | Low viscosity, fast curing binder for cellulose |
JPH0734023Y2 (en) | 1989-04-17 | 1995-08-02 | 川崎重工業株式会社 | Weighing and transporting device for powder and granules |
US5037930A (en) | 1989-09-22 | 1991-08-06 | Gaf Chemicals Corporation | Heterocyclic quaternized nitrogen-containing cellulosic graft polymers |
DE358282T1 (en) | 1989-11-08 | 1990-09-06 | Shell Internationale Research Maatschappij B.V., Den Haag/S'gravenhage | SOFT FLEXIBLE POLYURETHANE FOAMS, METHOD FOR THE PRODUCTION THEREOF AND POLYOL COMPOSITION USED IN THIS METHOD. |
JP2515411B2 (en) * | 1989-12-01 | 1996-07-10 | 新王子製紙株式会社 | Method for manufacturing thermal recording material |
US5151465A (en) | 1990-01-04 | 1992-09-29 | Arco Chemical Technology, L.P. | Polymer compositions and absorbent fibers produced therefrom |
DE69111480T2 (en) | 1990-02-14 | 1996-03-14 | Shinsozai Sogo Kenkyusho Kk | Filled and sealed, independent mixing container. |
DK0445578T3 (en) | 1990-03-03 | 1994-11-21 | Basf Ag | moldings |
US5041595A (en) | 1990-09-26 | 1991-08-20 | Union Carbide Chemicals And Plastics Technology Corporation | Method for manufacturing vinylalkoxysilanes |
US6495656B1 (en) | 1990-11-30 | 2002-12-17 | Eastman Chemical Company | Copolyesters and fibrous materials formed therefrom |
DE69034003T2 (en) | 1990-12-28 | 2003-05-22 | K C Shen Technology Internat L | Thermosetting resin and composite made of lignocellulosic material |
GB9108604D0 (en) | 1991-04-22 | 1991-06-05 | Nadreph Ltd | Gel products and a process for making them |
US5143582A (en) † | 1991-05-06 | 1992-09-01 | Rohm And Haas Company | Heat-resistant nonwoven fabrics |
US5128407A (en) | 1991-07-25 | 1992-07-07 | Miles Inc. | Urea extended polyisocyanates |
DE4127733A1 (en) | 1991-08-22 | 1993-02-25 | Basf Ag | Graft polymers of natural substances containing saccharide structures or derivatives thereof and ethylenically unsaturated compounds and their use. |
GB9126828D0 (en) | 1991-12-18 | 1992-02-19 | British American Tobacco Co | Improvements relating to smoking articles |
DE4202248A1 (en) | 1992-01-28 | 1993-07-29 | Belland Ag | METHOD FOR RECOVERY OF POLYMERS SOLVED IN AQUEOUS ALKALINE OR ACID MILIEU |
US5550189A (en) | 1992-04-17 | 1996-08-27 | Kimberly-Clark Corporation | Modified polysaccharides having improved absorbent properties and process for the preparation thereof |
US6077883A (en) | 1992-05-19 | 2000-06-20 | Johns Manville International, Inc. | Emulsified furan resin based glass fiber binding compositions, process of binding glass fibers, and glass fiber compositions |
AU5347294A (en) | 1992-05-19 | 1994-01-04 | Schuller International, Inc. | Glass fiber binding compositions, process of binding glass fibers, and glass fiber compositions |
US5661213A (en) | 1992-08-06 | 1997-08-26 | Rohm And Haas Company | Curable aqueous composition and use as fiberglass nonwoven binder |
US5434233A (en) | 1992-08-12 | 1995-07-18 | Kiely; Donald E. | Polyaldaramide polymers useful for films and adhesives |
US5300192A (en) | 1992-08-17 | 1994-04-05 | Weyerhaeuser Company | Wet laid fiber sheet manufacturing with reactivatable binders for binding particles to fibers |
US5308896A (en) | 1992-08-17 | 1994-05-03 | Weyerhaeuser Company | Particle binders for high bulk fibers |
AU5019993A (en) | 1992-08-17 | 1994-03-15 | Weyerhaeuser Company | Particle binders |
US5547541A (en) | 1992-08-17 | 1996-08-20 | Weyerhaeuser Company | Method for densifying fibers using a densifying agent |
US5352480A (en) | 1992-08-17 | 1994-10-04 | Weyerhaeuser Company | Method for binding particles to fibers using reactivatable binders |
FR2694894B1 (en) | 1992-08-20 | 1994-11-10 | Coletica | Use of a transacylation reaction between an esterified polysaccharide and a polyamine or polyhydroxylated substance for the manufacture of microparticles, process and composition. |
US5376614A (en) | 1992-12-11 | 1994-12-27 | United Technologies Corporation | Regenerable supported amine-polyol sorbent |
US5545279A (en) | 1992-12-30 | 1996-08-13 | Hall; Herbert L. | Method of making an insulation assembly |
BR9406219A (en) | 1993-01-23 | 1996-01-09 | Helmut Schiwek | Glass fiber production process and installation |
IL104734A0 (en) | 1993-02-15 | 1993-06-10 | Univ Bar Ilan | Bioactive conjugates of cellulose with amino compounds |
DE69413434T2 (en) | 1993-02-26 | 1999-04-01 | Mitsui Chemicals Inc | Resins for electrophotographic developers |
US5981719A (en) | 1993-03-09 | 1999-11-09 | Epic Therapeutics, Inc. | Macromolecular microparticles and methods of production and use |
US6090925A (en) | 1993-03-09 | 2000-07-18 | Epic Therapeutics, Inc. | Macromolecular microparticles and methods of production and use |
US5929184A (en) | 1993-06-02 | 1999-07-27 | Geltex Pharmaceuticals, Inc. | Hydrophilic nonamine-containing and amine-containing copolymers and their use as bile acid sequestrants |
US5340868A (en) | 1993-06-21 | 1994-08-23 | Owens-Corning Fiberglass Technology Inc. | Fibrous glass binders |
US5318990A (en) | 1993-06-21 | 1994-06-07 | Owens-Corning Fiberglas Technology Inc. | Fibrous glass binders |
JP3399588B2 (en) * | 1993-07-20 | 2003-04-21 | 東洋紡績株式会社 | Ink for writing implements |
EP0739320B1 (en) | 1993-09-29 | 1999-12-08 | W.R. Grace & Co.-Conn. | Improved cement admixture product having improved rheological properties and process of forming same |
US5393849A (en) | 1993-10-19 | 1995-02-28 | Georgia-Pacific Resins, Inc. | Curable polyester/polyamino compositions |
JP2811540B2 (en) | 1993-10-20 | 1998-10-15 | 呉羽化学工業株式会社 | Gas barrier film and method for producing the same |
DE4408688A1 (en) | 1994-03-15 | 1995-09-21 | Basf Ag | Formaldehyde-free binding, impregnating or coating compositions for fibrous webs |
US5955448A (en) | 1994-08-19 | 1999-09-21 | Quadrant Holdings Cambridge Limited | Method for stabilization of biological substances during drying and subsequent storage and compositions thereof |
GB9411080D0 (en) | 1994-06-02 | 1994-07-20 | Unilever Plc | Treatment |
DE4432899A1 (en) | 1994-09-15 | 1996-03-21 | Wacker Chemie Gmbh | Crosslinkable polymer powder compositions |
DE19581850T1 (en) | 1994-11-21 | 1997-10-16 | Asahi Chemical Ind | Polymer composite material |
EP0754656B1 (en) | 1995-02-07 | 2004-09-15 | Daicel-Degussa Ltd. | Cement setting retarder and cement setting retarder sheet |
DE59500267D1 (en) | 1995-03-24 | 1997-07-03 | Giulini Chemie | Amphoteric polymer dispersion, process for its preparation and its use |
US5919831A (en) | 1995-05-01 | 1999-07-06 | Philipp; Warren H. | Process for making an ion exchange material |
US5562740A (en) | 1995-06-15 | 1996-10-08 | The Procter & Gamble Company | Process for preparing reduced odor and improved brightness individualized, polycarboxylic acid crosslinked fibers |
US5720796A (en) | 1995-08-08 | 1998-02-24 | W. R. Grace & Co.-Conn. | Process of using roll press grinding aid for granulated blast furnace slag |
US5942123A (en) | 1995-09-05 | 1999-08-24 | Mcardle; Blaise | Method of using a filter aid protein-polysaccharide complex composition |
ES2175168T3 (en) | 1995-11-28 | 2002-11-16 | Kimberly Clark Co | COLOR COMPOUNDS STABILIZED BY LIGHT. |
US5788243A (en) | 1996-01-23 | 1998-08-04 | Harshaw; Bob F. | Biodegradable target |
DE19606394A1 (en) | 1996-02-21 | 1997-08-28 | Basf Ag | Formaldehyde-free, aqueous binders |
EP0900367A1 (en) | 1996-04-12 | 1999-03-10 | Oncor, Inc. | Method and composition for controlling formaldehyde fixation by delayed quenching |
US6072086A (en) | 1996-04-12 | 2000-06-06 | Intergen Company | Method and composition for controlling formaldehyde fixation by delayed quenching |
DE19621573A1 (en) | 1996-05-29 | 1997-12-04 | Basf Ag | Thermally curable, aqueous compositions |
AU742125B2 (en) | 1996-08-21 | 2001-12-20 | Rohm And Haas Company | A formaldehyde-free, accelerated cure aqueous composition for bonding glass fiber-heat resistant nonwovens |
US20020161108A1 (en) | 2000-03-09 | 2002-10-31 | Stepan Company, A Corporation Of The State Of Delaware | Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids |
US6310227B1 (en) | 1997-01-31 | 2001-10-30 | The Procter & Gamble Co. | Reduced calorie cooking and frying oils having improved hydrolytic stability, and process for preparing |
US5932665A (en) | 1997-02-06 | 1999-08-03 | Johns Manville International, Inc. | Polycarboxy polymer acid binders having reduced cure temperatures |
CN1089727C (en) | 1997-04-11 | 2002-08-28 | 广州市环境保护科学研究所 | Method for preparing cation/amphoteric graft polyacrylamide flocculating agent |
TW408152B (en) | 1997-04-25 | 2000-10-11 | Rohm & Haas | Formaldehyde-free curable composition and method for bonding heat-resistant fibers of a nonwoven material by using the composition |
ES2189174T3 (en) | 1997-05-02 | 2003-07-01 | Ledertech Gmbh | THERMOPLASTIC COMPOSITE MATERIAL. |
DE19729161A1 (en) | 1997-07-08 | 1999-01-14 | Basf Ag | Thermally curable, aqueous compositions |
US5977232A (en) | 1997-08-01 | 1999-11-02 | Rohm And Haas Company | Formaldehyde-free, accelerated cure, aqueous composition for bonding glass fiber heat-resistant nonwovens |
DE19735959A1 (en) | 1997-08-19 | 1999-02-25 | Basf Ag | Thermally curable, aqueous binding agent composition |
US5895804A (en) | 1997-10-27 | 1999-04-20 | National Starch And Chemical Investment Holding Corporation | Thermosetting polysaccharides |
US5983586A (en) | 1997-11-24 | 1999-11-16 | Owens Corning Fiberglas Technology, Inc. | Fibrous insulation having integrated mineral fibers and organic fibers, and building structures insulated with such fibrous insulation |
US6171654B1 (en) * | 1997-11-28 | 2001-01-09 | Seydel Research, Inc. | Method for bonding glass fibers with cross-linkable polyester resins |
NL1008041C2 (en) † | 1998-01-16 | 1999-07-19 | Tidis B V I O | Application of a water-soluble binder system for the production of glass or rock wool. |
DE69909454T3 (en) | 1998-03-19 | 2009-09-10 | Rockwool International A/S | Method and device for producing a mineral fiber product |
US6140445A (en) | 1998-04-17 | 2000-10-31 | Crompton Corporation | Silane functional oligomer |
ES2343604T3 (en) | 1998-05-18 | 2010-08-04 | Knauf Fiber Glass Gmbh | GLASS FIBER BINDING COMPOSITIONS AND PROCEDURE FOR THE SAME. |
JP3907837B2 (en) | 1998-06-12 | 2007-04-18 | 富士フイルム株式会社 | Image recording material |
US6468668B1 (en) | 1998-09-14 | 2002-10-22 | Canon Kabushiki Kaisha | Cellulosic composite product and a method of producing the same |
US6331350B1 (en) | 1998-10-02 | 2001-12-18 | Johns Manville International, Inc. | Polycarboxy/polyol fiberglass binder of low pH |
EP0990727A1 (en) * | 1998-10-02 | 2000-04-05 | Johns Manville International Inc. | Polycarboxy/polyol fiberglass binder |
US6231721B1 (en) | 1998-10-09 | 2001-05-15 | Weyerhaeuser Company | Compressible wood pulp product |
US6201472B1 (en) * | 1998-10-26 | 2001-03-13 | Pittway Corp. | Wireless communication system with increased dynamic range |
EP1038433B1 (en) | 1999-03-19 | 2008-06-04 | Saint-Gobain Cultilene B.V. | Substrate for soilless cultivation |
US6440204B1 (en) | 1999-03-31 | 2002-08-27 | Penford Corporation | Packaging and structural materials comprising potato peel waste |
US6210472B1 (en) | 1999-04-08 | 2001-04-03 | Marconi Data Systems Inc. | Transparent coating for laser marking |
US7029717B1 (en) | 1999-04-16 | 2006-04-18 | San-Ei Gen F.F.I., Inc. | Sucralose-containing composition and edible products containing the composition |
WO2001007532A1 (en) | 1999-07-26 | 2001-02-01 | Minnesota Corn Processors Llc | De-icing composition and method |
EP1164163A1 (en) † | 2000-06-16 | 2001-12-19 | Rockwool International A/S | Binder for mineral wool products |
EP1170265A1 (en) † | 2000-07-04 | 2002-01-09 | Rockwool International A/S | Binder for mineral wool products |
DE60112527T2 (en) | 2000-09-20 | 2006-06-01 | Celanese International Corp., Dallas | Crosslinker systems of monohydroxyalkylurea and polysaccharide |
US6379739B1 (en) | 2000-09-20 | 2002-04-30 | Griffith Laboratories Worldwide, Inc. | Acidulant system for marinades |
US6613378B1 (en) | 2000-10-18 | 2003-09-02 | The United States Of America As Represented By The Secretary Of Agriculture | Sugar-based edible adhesives |
US6525009B2 (en) | 2000-12-07 | 2003-02-25 | International Business Machines Corporation | Polycarboxylates-based aqueous compositions for cleaning of screening apparatus |
DE10101944A1 (en) | 2001-01-17 | 2002-07-18 | Basf Ag | A new binder for finely divided materials, useful for preparation of flat-shaped articles from finely divided materials, comprises the reaction product of di or tricarboxylic acid or its anhydride with ammonia |
US7816514B2 (en) | 2001-02-16 | 2010-10-19 | Cargill, Incorporated | Glucosamine and method of making glucosamine from microbial biomass |
JP3750552B2 (en) | 2001-03-28 | 2006-03-01 | 日東紡績株式会社 | Method for producing glass fiber wound body and method for producing glass fiber fabric |
US7157524B2 (en) * | 2001-05-31 | 2007-01-02 | Owens Corning Fiberglas Technology, Inc. | Surfactant-containing insulation binder |
JP2004060058A (en) | 2002-07-24 | 2004-02-26 | Mitsubishi Heavy Ind Ltd | Fiber substrate for composite material |
TWI331526B (en) | 2001-09-21 | 2010-10-11 | Bristol Myers Squibb Pharma Co | Lactam-containing compounds and derivatives thereof as factor xa inhibitors |
US6858074B2 (en) | 2001-11-05 | 2005-02-22 | Construction Research & Technology Gmbh | High early-strength cementitious composition |
JP3787085B2 (en) | 2001-12-04 | 2006-06-21 | 関東化学株式会社 | Composition for removing photoresist residue |
ATE328973T1 (en) | 2002-02-20 | 2006-06-15 | Du Pont | PAINTS WITH HIGHLY BRANCHED COPOLYESTER POLYOL |
ATE443996T1 (en) | 2002-02-22 | 2009-10-15 | Genencor Int | TANNING PRODUCTS |
US6955844B2 (en) | 2002-05-24 | 2005-10-18 | Innovative Construction And Building Materials | Construction materials containing surface modified fibers |
AU2003237324B8 (en) | 2002-06-18 | 2009-12-10 | Georgia-Pacific Chemicals Llc | Polyester-type formaldehyde free insulation binder |
EP1382642A1 (en) | 2002-07-15 | 2004-01-21 | Rockwool International A/S | Formaldehyde-free aqueous binder composition for mineral fibers |
US6887961B2 (en) | 2002-07-26 | 2005-05-03 | Kimberly-Clark Worldwide, Inc. | Absorbent binder composition and method of making it |
US7384881B2 (en) * | 2002-08-16 | 2008-06-10 | H.B. Fuller Licensing & Financing, Inc. | Aqueous formaldehyde-free composition and fiberglass insulation including the same |
TW200411218A (en) | 2002-08-22 | 2004-07-01 | Shy-Shiun Chern | Optical switch |
US7090745B2 (en) | 2002-09-13 | 2006-08-15 | University Of Pittsburgh | Method for increasing the strength of a cellulosic product |
US20060135433A1 (en) | 2002-10-08 | 2006-06-22 | Murray Christopher J | Phenolic binding peptides |
US6818694B2 (en) | 2002-10-10 | 2004-11-16 | Johns Manville International, Inc. | Filler extended fiberglass binder |
US7141626B2 (en) | 2002-10-29 | 2006-11-28 | National Starch And Chemical Investment Holding Corporation | Fiberglass non-woven catalyst |
US6699945B1 (en) | 2002-12-03 | 2004-03-02 | Owens Corning Fiberglas Technology, Inc. | Polycarboxylic acid based co-binder |
US7026390B2 (en) | 2002-12-19 | 2006-04-11 | Owens Corning Fiberglas Technology, Inc. | Extended binder compositions |
US7201778B2 (en) | 2003-01-13 | 2007-04-10 | North Carolina State University | Ionic cross-linking of ionic cotton with small molecular weight anionic or cationic molecules |
US6884849B2 (en) | 2003-02-21 | 2005-04-26 | Owens-Corning Fiberglas Technology, Inc. | Poly alcohol-based binder composition |
US7056563B2 (en) | 2003-04-04 | 2006-06-06 | Weyerhaeuser Company | Hot cup made from an insulating paperboard |
US7947766B2 (en) | 2003-06-06 | 2011-05-24 | The Procter & Gamble Company | Crosslinking systems for hydroxyl polymers |
US20040254285A1 (en) | 2003-06-12 | 2004-12-16 | Rodrigues Klein A. | Fiberglass nonwoven binder |
AU2004201002B2 (en) | 2003-08-26 | 2009-08-06 | Rohm And Haas Company | Curable aqueous composition and use as heat-resistant nonwoven binder |
US20050059770A1 (en) * | 2003-09-15 | 2005-03-17 | Georgia-Pacific Resins Corporation | Formaldehyde free insulation binder |
DE10342858A1 (en) | 2003-09-15 | 2005-04-21 | Basf Ag | Use of formaldehyde-free aqueous binders for substrates |
US20070009582A1 (en) | 2003-10-07 | 2007-01-11 | Madsen Niels J | Composition useful as an adhesive and use of such a composition |
US20050208095A1 (en) | 2003-11-20 | 2005-09-22 | Angiotech International Ag | Polymer compositions and methods for their use |
US7842382B2 (en) | 2004-03-11 | 2010-11-30 | Knauf Insulation Gmbh | Binder compositions and associated methods |
US20050215153A1 (en) | 2004-03-23 | 2005-09-29 | Cossement Marc R | Dextrin binder composition for heat resistant non-wovens |
US6977116B2 (en) | 2004-04-29 | 2005-12-20 | The Procter & Gamble Company | Polymeric structures and method for making same |
US20060099870A1 (en) | 2004-11-08 | 2006-05-11 | Garcia Ruben G | Fiber mat bound with a formaldehyde free binder, asphalt coated mat and method |
KR100712970B1 (en) | 2005-03-03 | 2007-05-02 | 롬 앤드 하아스 컴패니 | Method for reducing corrosion |
CA2607611C (en) | 2005-05-06 | 2013-11-26 | Dynea Oy | Poly (vinyl alcohol) - based formaldehyde-free curable aqueous composition |
DE102005029479A1 (en) | 2005-06-24 | 2007-01-04 | Saint-Gobain Isover G+H Ag | Process for producing bonded mineral wool and binder therefor |
EP1741726A1 (en) | 2005-07-08 | 2007-01-10 | Rohm and Haas France SAS | Curable aqueous composition and use as water repellant fiberglass nonwoven binder |
KR20220062129A (en) | 2005-07-26 | 2022-05-13 | 크나우프 인설레이션, 인크. | Binders and materials made therewith |
EP1917319B1 (en) | 2005-08-26 | 2011-03-16 | Asahi Fiber Glass Company, Limited | Aqueous binder for inorganic fiber and thermal and/or acoustical insulation material using the same |
US7803879B2 (en) | 2006-06-16 | 2010-09-28 | Georgia-Pacific Chemicals Llc | Formaldehyde free binder |
US9169157B2 (en) | 2006-06-16 | 2015-10-27 | Georgia-Pacific Chemicals Llc | Formaldehyde free binder |
US7795354B2 (en) | 2006-06-16 | 2010-09-14 | Georgia-Pacific Chemicals Llc | Formaldehyde free binder |
UA99115C2 (en) | 2006-11-03 | 2012-07-25 | Дайнеа Ой | Aqueous curable composition, process for its preparation, process for binding of non-woven fibers, bound non-woven product and heat insulation of buildings |
WO2008089851A1 (en) | 2007-01-25 | 2008-07-31 | Knauf Insulation Limited | Formaldehyde-free mineral fibre insulation product |
US9828287B2 (en) | 2007-01-25 | 2017-11-28 | Knauf Insulation, Inc. | Binders and materials made therewith |
EP2137223B1 (en) | 2007-04-13 | 2019-02-27 | Knauf Insulation GmbH | Composite maillard-resole binders |
PE20100438A1 (en) | 2008-06-05 | 2010-07-14 | Georgia Pacific Chemicals Llc | COMPOSITION OF AQUEOUS SUSPENSION WITH PARTICLES OF VALUABLE MATERIALS AND IMPURITIES |
-
2004
- 2004-10-13 US US10/965,359 patent/US7842382B2/en not_active Expired - Fee Related
-
2005
- 2005-03-10 EA EA200601663A patent/EA013372B1/en not_active IP Right Cessation
- 2005-03-10 PT PT05725278T patent/PT1732968E/en unknown
- 2005-03-10 PL PL05725278T patent/PL1732968T3/en unknown
- 2005-03-10 JP JP2007503025A patent/JP2007528438A/en active Pending
- 2005-03-10 CA CA2558981A patent/CA2558981C/en not_active Expired - Fee Related
- 2005-03-10 AT AT05725278T patent/ATE512182T1/en active
- 2005-03-10 MX MXPA06010302A patent/MXPA06010302A/en active IP Right Grant
- 2005-03-10 DK DK05725278.5T patent/DK1732968T3/en active
- 2005-03-10 WO PCT/US2005/008018 patent/WO2005087837A1/en active Application Filing
- 2005-03-10 SI SI200531326T patent/SI1732968T1/en unknown
- 2005-03-10 EP EP05725278.5A patent/EP1732968B2/en active Active
- 2005-03-10 EP EP20100184926 patent/EP2392605A3/en not_active Withdrawn
-
2006
- 2006-09-01 NO NO20063916A patent/NO20063916L/en not_active Application Discontinuation
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2010
- 2010-11-05 US US12/940,597 patent/US8691934B2/en active Active
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2011
- 2011-07-05 HR HR20110499T patent/HRP20110499T1/en unknown
-
2014
- 2014-03-18 US US14/217,604 patent/US20140197349A1/en not_active Abandoned
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2016
- 2016-06-20 US US15/186,873 patent/US20160297923A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
ATE512182T1 (en) | 2011-06-15 |
CA2558981C (en) | 2015-06-16 |
US20140197349A1 (en) | 2014-07-17 |
WO2005087837A1 (en) | 2005-09-22 |
EA200601663A1 (en) | 2007-02-27 |
PT1732968E (en) | 2011-07-25 |
EP1732968B1 (en) | 2011-06-08 |
EP2392605A3 (en) | 2014-02-19 |
US20050202224A1 (en) | 2005-09-15 |
JP2007528438A (en) | 2007-10-11 |
EP1732968A1 (en) | 2006-12-20 |
HRP20110499T1 (en) | 2011-09-30 |
EA013372B1 (en) | 2010-04-30 |
NO20063916L (en) | 2006-10-24 |
MXPA06010302A (en) | 2006-12-14 |
US20110054143A1 (en) | 2011-03-03 |
EP2392605A2 (en) | 2011-12-07 |
DK1732968T3 (en) | 2011-08-01 |
CA2558981A1 (en) | 2005-09-22 |
SI1732968T1 (en) | 2011-10-28 |
US7842382B2 (en) | 2010-11-30 |
PL1732968T3 (en) | 2011-11-30 |
EP1732968B2 (en) | 2016-01-06 |
US8691934B2 (en) | 2014-04-08 |
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Legal Events
Date | Code | Title | Description |
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STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- INCOMPLETE APPLICATION (PRE-EXAMINATION) |