Water-based binder composition

Abstract

An aqueous binder composition is disclosed that includes at least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 daltons; a primary crosslinker that includes at least two carboxylic acid groups; and a secondary crosslinker that includes a short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 daltons.

Description

Technical Field

[0001] This application claims the priority and benefit of U.S. Provisional Patent Application No. 62 / 831,222, filed on April 9, 2019, the entire content of which is incorporated herein by reference.

Background Art

[0002] Aqueous binder compositions have traditionally been used in the formation of woven and non-woven fibrous products such as insulation products, composite products, and wood fiber boards. Insulation products such as fiberglass and mineral wool insulation products are typically manufactured by fiberizing a molten composition of a polymer, glass, or other mineral and spinning the fine fibers from a fiberizing device such as a rotary spinner. To form an insulation product, the fibers produced by the rotary spinner are drawn downward from the spinner to a conveyor by a blower. As the fibers move downward, a binder material is sprayed onto the fibers, and the fibers are collected into a thick continuous blanket on the conveyor. The binder material imparts elasticity for post-packaging recovery of the insulation product and gives rigidity and handleability so that the insulation product can be handled and applied in the insulation cavities of a building as needed. The binder composition also protects the fibers from wear between filaments and promotes compatibility between individual fibers. The blanket containing the binder-coated fibers is then passed through a curing oven, the binder cures, and the blanket is set to the desired thickness. Once the binder has cured, the fiber insulation can be cut to length to form individual insulation products, which can be packaged and shipped to the customer's location.

[0003] The fiber glass insulation products prepared in this way can be provided in various forms including bats, blankets and boards (heated and compressed bats) for use in various applications. The bat of binder-coated fibers is likely to expand due to the elasticity of the glass fibers as it exits the forming chamber. Typically, the expanded bat is then conveyed to and passed through a curing oven where the binder cures as hot air passes through the insulation product. In addition to the curing of the binder, in the curing oven, the insulation product is compressed by flights or rollers so that the resulting blanket, bat or board product can be of the desired dimensions and have the desired surface finish. Phenol-formaldehyde (PF) binder compositions as well as urea-extended PF resins (PUF resins) have been traditionally used in the manufacture of fiber glass insulation products. In insulation boards, known also as "high density" products, such as ceiling boards, duct traps, duct liners, etc., phenol-formaldehyde binder technology has been utilized to produce high density products with inexpensive and acceptable physical and mechanical properties. However, formaldehyde binders emit undesirable emissions during the manufacture of fiber glass insulation. As an alternative to formaldehyde-based binders, certain formaldehyde-free formulations have been developed for use as binders in fiber glass insulation products. However, one of the challenges in developing suitable alternatives is to identify formulations that have equivalent mechanical and physical properties while avoiding undesirable properties such as discoloration. Such property challenges include high temperature / high humidity performance, stiffness, adhesion strength, processability (viscosity, cutting, grinding, edge coating), and obtaining a bright color without yellowing. Accordingly, there is a need for environmentally friendly formaldehyde-free binder compositions that are used to manufacture insulation products without compromising their physical and mechanical properties. SUMMARY OF THE INVENTION

[0004] Various exemplary aspects of the inventive concept are directed to an aqueous binder composition comprising a crosslinking agent containing at least 35% by weight, based on the total solids content of the aqueous binder composition, of at least two carboxylic acid groups, at least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 Daltons in an amount of 0.1 to 50.0% by weight, based on the total solids content of the aqueous binder composition; and optionally, at least one short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 Daltons. The binder composition, upon curing, contains 6.0% by weight or less of water-soluble substances.

[0005] In some exemplary embodiments, the crosslinking agent is a polymeric polycarboxylic acid, such as a homopolymer or copolymer of acrylic acid. The crosslinking agent may be present in the binder composition in an amount of 50% to 85% by weight, based on the total solids content of the aqueous binder composition. In some exemplary embodiments, the crosslinking agent is present in the binder composition in an amount of 65% to 80% by weight, based on the total solids content of the aqueous binder composition. In various exemplary embodiments, the short-chain polyol is present in the binder composition in an amount of 1.0% to 50% by weight, based on the total solids content of the aqueous binder composition. In various exemplary embodiments, the short-chain polyol includes one or more of sugar alcohols, 2,2-bis(methylol)propionic acid, tris(methylol)propane, and short-chain alkanolamines. When the short-chain polyol includes a sugar alcohol, the sugar alcohol may be selected from the group consisting of glycerol, erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, iditol, isomaltitol, lactitol, cellobiitol, palatinite, maltotriitol, their syrups, and mixtures thereof.

[0006] In some exemplary embodiments, the long-chain polyol is selected from the group consisting of partially or fully hydrolyzed polyvinyl alcohol and polyvinyl acetate. The long-chain polyol may be present in the binder composition in an amount of 1% to 30% by weight based on the total solids content of the aqueous binder composition. In various exemplary embodiments, the ratio of long-chain polyol to short-chain polyol is between 1 / 50 and 20 / 1. In various exemplary embodiments, the binder composition has a water-soluble substance content of 5.0% by weight or less after curing.

[0007] Another exemplary aspect of the inventive concept is directed to an aqueous binder composition comprising at least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 daltons in an amount of 0.1 to 50% by weight based on the total solids content of the aqueous binder composition; a crosslinking agent comprising at least two carboxylic acid groups in an amount of at least 35% by weight based on the total solids content of the aqueous binder composition; and at least one short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 daltons in an amount of 1.0 to 50% by weight. The binder composition includes a ratio of the molar equivalent of carboxylic acid groups, anhydride groups or salts thereof to the molar equivalent of hydroxyl groups of 1 / 0.05 to 1 / 20, and a ratio of long-chain polyol to short-chain polyol between 1 / 50 and 20 / 1.

[0008] Other exemplary aspects of the inventive concept are directed to fibrous products comprising a plurality of randomly oriented fibers and an aqueous binder composition that at least partially coats the fibers. The binder composition comprises a crosslinking agent comprising at least 35 wt% based on the total solids content of the aqueous binder composition, at least two carboxylic acid groups, at least 0.1 to 50.0 wt% based on the total solids content of the aqueous binder composition, at least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 daltons; and optionally, at least one short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 daltons. The binder composition, when cured, comprises 6.0 wt% or less of water-soluble substances.

[0009] The fibers of the insulation product may comprise one or more of mineral fibers, natural fibers, and synthetic fibers, and in some embodiments, the fibers comprise glass fibers. In some exemplary embodiments, the fibrous product comprises any of an insulation product, a nonwoven mat, a particle board, a ceiling board, a duct board, and the like. Numerous other aspects, advantages and / or features of the general inventive concept will become more readily apparent from the following detailed description of the exemplary embodiments and the accompanying drawings submitted herewith. The general concept of the invention as well as its illustrative embodiments and advantages are described in detail below by way of example with reference to the drawings.

Brief Description of the Drawings

[0010]

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MODE FOR CARRYING OUT THE INVENTION

[0011] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the exemplary embodiments belong. The terms used in the description herein are for the purpose of describing the exemplary embodiments only and are not intended to limit the exemplary embodiments. Accordingly, the general concepts of the present invention are not intended to be limited to the specific embodiments illustrated herein. Although other methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein. As used in this specification and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0012] Unless otherwise indicated, it should be understood that all numbers expressing quantities of ingredients, chemical and molecular properties, reaction conditions, etc. used in this specification and the claims are modified in all instances by the term "about". Accordingly, unless otherwise indicated, the numerical parameters set forth in this specification and the appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the exemplary embodiments of the present invention. Each numerical parameter should at least be construed in light of the number of significant digits and the ordinary rounding method. Although the numerical ranges and parameters setting forth the broad scope of the exemplary embodiments are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors resulting from the standard deviation found in the respective test measurements. All numerical ranges given throughout this specification and the claims include all such narrower numerical ranges that fall within such broader numerical ranges as if each such narrower numerical range were explicitly set forth herein.

[0013] The present disclosure relates to a formaldehyde-free aqueous binder composition for use in the manufacture of insulation products having equivalent or improved mechanical and physical properties compared to products manufactured using traditional formaldehyde-based binder compositions. The formaldehyde-free binder composition can be used in the manufacture of fiber insulation products and related products made from cured formaldehyde-free binders, such as thin fiber reinforced mats (hereinafter all collectively referred to as fiber reinforced products) and glass fiber or mineral wool products, particularly fiber glass or mineral wool insulation products. Other products can include composite products, wood fiber board products, insulation for metal buildings, pipe insulation, ceiling boards, ceiling tiles, "high density" products such as ceiling boards, duct traps, duct liners, and further "low density" products. Further fibrous products include non-woven fiber mats, and particle boards and composite products manufactured therefrom.

[0014] In some exemplary embodiments, the formaldehyde-free aqueous binder composition includes at least one primary crosslinking agent, at least one secondary crosslinking agent including at least one short-chain polyol, and at least one long-chain polyol. The primary crosslinking agent may be any compound suitable for crosslinking a polyol. In an exemplary embodiment, the primary crosslinking agent has a number average molecular weight greater than 90 Daltons, from 90 Daltons to 10,000 Daltons, or from 190 Daltons to 5,000 Daltons. In some exemplary embodiments, the crosslinking agent has a number average molecular weight from 2,000 Daltons to 5,000 Daltons, or 4,000 Daltons. Non-limiting examples of suitable crosslinking agents include one or more carboxylic acid groups (-COOH), such as polycarboxylic acids (and their salts), acid anhydrides, monomeric and polymeric polycarboxylic acids having acid anhydrides (i.e., mixed acid anhydrides), and homopolymers or copolymers of acrylic acid, such as polyacrylic acid (and its salts), and polyacrylic acid-based resins, such as materials having QR-1629S and Acumer 9932, both commercially available from The Dow Chemical Company. Acumer 9932 is a polyacrylic acid / sodium hypophosphite resin having a molecular weight of 4000 and a sodium hypophosphite content of 6 - 7% by weight. QR-1629S is a polyacrylic acid / glycerin mixture.

[0015] In some cases, the primary crosslinking agent may be pre-neutralized with a neutralizing agent. Such neutralizing agents include organic and / or inorganic bases, such as sodium hydroxide, ammonium hydroxide, and diethylamine, and any type of primary, secondary, or tertiary amine (including alkanolamines). In various exemplary embodiments, the neutralizing agent may include at least one of sodium hydroxide and triethanolamine. In some exemplary embodiments, the primary crosslinking agent is present in the aqueous binder composition in an amount of at least 50% by weight, such as, without limitation, at least 55% by weight, at least 60% by weight, at least 63% by weight, at least 65% by weight, at least 70% by weight, at least 73% by weight, at least 75% by weight, at least 78% by weight, and at least 80% by weight, based on the total solids content of the aqueous binder composition. In some exemplary embodiments, the primary crosslinking agent is present in the aqueous binder composition in an amount of 50% to 85% by weight, including all end points and partial combinations therebetween, such as, without limitation, 60% to 80% by weight, 62% to 78% by weight, and 65% to 75% by weight, based on the total solids content of the aqueous binder composition.

[0016] In some exemplary embodiments, the long-chain polyol includes a polyol having at least two hydroxyl groups with a number average molecular weight of at least 2,000 Daltons, such as a molecular weight of 3,000 Daltons to 4,000 Daltons. In some exemplary embodiments, the long-chain polyol includes one or more of a polymeric polyhydroxy compound, such as polyvinyl alcohol, polyvinyl acetate that may be partially or fully hydrolyzed, or a mixture thereof. By way of illustration, when partially hydrolyzed polyvinyl acetate acts as the polyhydroxy component, polyvinyl acetate hydrolyzed to 80% to 89%, such as Poval® 385 and Selvol® 502, both hydrolyzed to 85% (Poval® 385) and 88% (Selvol® 502), respectively, such as Poval® 385 (Kuraray America, Inc.) and Sevol® 502 (Sekisui Specialty Chemicals America, LLC), etc., can be utilized. The long-chain polyol may be present in the aqueous binder composition in an amount of up to 50% by mass of the total solids, for example, without limitation, up to 40% by mass, 35% by mass, 30% by mass, 28% by mass, 25% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass of the total solids. In some exemplary embodiments, the long-chain polyol is present in the aqueous binder composition in an amount of 0.1 to 50% by mass of the total solids, for example, without limitation, including all end points and partial combinations therebetween, in an amount of 0.5% by mass to 30% by mass, 1% by mass to 20% by mass, 5% by mass to 18% by mass, and 7% by mass to 15% by mass of the total solids.

[0017] The aqueous binder composition may include a secondary cross-linking agent such as a short-chain polyol. The short-chain polyol has a molecular weight of less than 2,000 Daltons, for example, less than 750 Daltons, less than 500 Daltons, and may include a water-soluble compound having a plurality of hydroxyl (-OH) groups. Suitable short-chain polyol components include sugar alcohols, 2,2-bis(methylol)propionic acid (bis-MPA), tri(methylol)propane (TMP), pentaerythritol, and short-chain alkanolamines such as triethanolamine. In some exemplary embodiments, the short-chain polyol acts as a viscosity reducer and reduces the viscosity of the composition by breaking the intramolecular and intermolecular hydrogen bonds between long-chain polyol molecules (e.g., polyvinyl alcohol). However, since these short-chain polyol molecules have a structure similar to that of the long-chain polyol, they can react with the cross-linking agent in the same way. Therefore, it does not adversely affect the performance of the binder and the product. Sugar alcohols are understood to mean compounds obtained when the aldehyde or keto group of a sugar is reduced to the corresponding hydroxy group (e.g., by hydrogenation). The starting sugar can be selected from monosaccharides, oligosaccharides and polysaccharides, as well as mixtures of their products, such as syrups, molasses and starch hydrolysates. Also, the starting sugar may be in the anhydrous form of the sugar. Sugar alcohols resemble the corresponding starting sugars but are not sugars. Thus, for example, sugar alcohols do not have reducing ability and cannot participate in the Maillard reaction typical of reducing sugars. In some exemplary embodiments, the sugar alcohol includes glycerol, erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, iditol, isomaltitol, lactitol, cellobiitol, palatinite, maltotriitol, their syrups, and mixtures thereof. In various exemplary embodiments, the sugar alcohol is selected from glycerol, sorbitol, xylitol and mixtures thereof. In some exemplary embodiments, the secondary crosslinking agent is a dimer or oligomer condensation product of a sugar alcohol. In various exemplary embodiments, the condensation product of the sugar alcohol is isosorbide. In some exemplary embodiments, the sugar alcohol is a diol or glycol.

[0018] In some exemplary embodiments, the short-chain polyol is present in the aqueous binder composition in an amount of up to 50% by mass of the total solids, for example, without limitation, up to 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 11% by mass and 10% by mass of the total solids. In some exemplary embodiments, the short-chain polyol is present in the aqueous binder composition in an amount of 0 to 50% by mass of the total solids, including all endpoints and partial combinations therebetween, for example, without limitation, 2% to 45% by mass, 1% to 35% by mass, 5% to 30% by mass, 7% to 27% by mass and 10% to 25% by mass of the total solids.

[0019] In various exemplary embodiments, the long-chain polyol, crosslinking agent, and short-chain polyol are present in amounts such that the ratio of the molar equivalent number of carboxylic acid groups, anhydride groups, or salts thereof to the molar equivalent number of hydroxyl groups is from 1 / 0.3 to 1 / 10, including 1 / 0.05 to 1 / 20, such as 1 / 0.1 to 1 / 5.0, 1 / 0.3 to 1 / 3, and 1 / 0.4 to 1 / 2.5. However, surprisingly, within this ratio range, it has been discovered that the ratio of the long-chain polyol to the short-chain polyol based on the molar equivalent of the hydroxyl group affects the performance of the binder composition, such as the tensile strength and water solubility of the cured binder. For example, it has been discovered that when the ratio of the long-chain polyol to the short-chain polyol is between 1 / 50 and 20 / 1, such as from 1 / 20 to 10 / 1, or from 1 / 10 to 5 / 1 - 2 / 11 / 1, balanced and desirable mechanical and physical properties can be obtained. In various exemplary embodiments, the ratio of the long-chain polyol to the short-chain polyol is approximately 1 / 30. The ratio of the long-chain polyol to the short-chain polyol may be optimized such that specific properties are optimized according to the needs of the end use. For example, decreasing the long-chain polyol concentration may also decrease the tensile strength of the product formed using the binder composition. However, when the long-chain polyol decreases, it may affect other properties, such as physical properties. Thus, unexpectedly, a balance between various properties has been found within the ratio ranges disclosed herein.

[0020] Surprisingly, long-chain polyols, such as polyvinyl alcohol, generally have the highest viscosity among all binder raw materials, but it has been found that the addition of a small amount of long-chain polyol actually decreases the overall binder viscosity. In some exemplary embodiments, the addition of a small amount of long-chain polyol (less than 0.1 to 20% by mass) decreases the viscosity of the binder solution by up to 50% relative to the viscosity of the binder composition excluding the long-chain polyol. Furthermore, it has been found that the addition of a small amount of long-chain polyol simultaneously increases the tensile / LOI strength by up to 40% compared to the tensile / LOI strength of the binder composition excluding the long-chain polyol, both under ambient conditions and high-temperature and high-humidity conditions.

[0021] The aqueous binder composition may contain an esterification catalyst that is also known as a curing accelerator. The catalyst may include inorganic salts, Lewis acids (i.e., aluminum chloride or boron trifluoride), Bronsted acids (i.e., sulfuric acid, p-toluenesulfonic acid, and boric acid), organometallic complexes (i.e., lithium carboxylate, sodium carboxylate), and / or Lewis bases (i.e., polyethyleneimine, diethylamine, or triethylamine). Further, the catalyst may include alkali metal salts of phosphorus-containing organic acids, particularly alkali metal salts of phosphoric acid, hypophosphorous acid, or polyphosphoric acid. Examples of such phosphorus catalysts include, but are not limited to, sodium hypophosphite, sodium phosphate, potassium phosphate, disodium pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium phosphate, potassium tripolyphosphate, sodium trimetaphosphate, sodium tetrametaphosphate, and mixtures thereof. Further, the catalyst or curing accelerator may be a fluoroborate compound, such as fluoroboric acid, sodium tetrafluoroborate, potassium tetrafluoroborate, calcium tetrafluoroborate, magnesium tetrafluoroborate, zinc tetrafluoroborate, ammonium tetrafluoroborate, and mixtures thereof. Further, the catalyst may be a mixture of a phosphorus compound and a fluoroborate compound. Other sodium salts, such as sodium sulfate, sodium nitrate, sodium carbonate, may also, or alternatively, be used as a catalyst.

[0022] The catalyst may be present in the aqueous binder composition in an amount of 0% to 10% by mass, for example, without limitation, 1% to 5% by mass, or 2% to 4.5% by mass, or 2.8% to 4.0% by mass, or 3.0% to 3.8% by mass, based on the total solids of the binder composition. The aqueous binder composition may contain at least one coupling agent. In at least one exemplary embodiment, the coupling agent is a silane coupling agent. The coupling agent may be present in the binder composition in an amount of 0.01% to 5% by mass, 0.01% to 2.5% by mass, 0.05% to 1.5% by mass, or 0.1% to 1.0% by mass of the total solids of the binder composition.

[0023] Non-limiting examples of silane coupling agents that can be used in the binder composition may be characterized by functional groups alkyl, aryl, amino, epoxy, vinyl, methacryloxy, ureido, isocyanate, and mercapto. In an exemplary embodiment, the silane coupling agent includes silanes containing one or more nitrogen atoms having one or more functional groups, such as amines (primary, secondary, tertiary, and quaternary), amino, imino, amide, imide, ureido, or isocyanate. Specific non-limiting examples of suitable silane coupling agents include, but are not limited to, aminosilanes (e.g., triethoxyaminopropylsilane, 3-aminopropyl-triethoxysilane, and 3-aminopropyl-trihydroxysilane), epoxy trialkoxysilanes (e.g., 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane), methacryl trialkoxysilanes (e.g., 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane), hydrocarbon trialkoxysilanes, aminotrihydroxysilane, epoxy trihydroxysilane, methacryl trihydroxysilane, and / or hydrocarbon trihydroxysilane. In one or more exemplary embodiments, the silane is an aminosilane, such as γ-aminopropyltriethoxysilane.

[0024] The aqueous binder composition may contain a processing aid. The processing aid is not particularly limited as long as it functions to promote fiber formation and orientation treatment. The processing aid is used to improve the coating distribution uniformity of the binder, reduce the viscosity of the binder, increase the gradient height after formation, improve the longitudinal mass distribution uniformity, and / or accelerate the dehydration of the binder in both the forming process and the oven curing process. The processing aid may be present in the binder composition in an amount of 0 to 10% by mass, 0.1% to 5.0% by mass, or 0.3% to 2.0% by mass, or 0.5% to 1.0% by mass based on the total solid content in the binder composition. In some exemplary embodiments, the aqueous binder composition is essentially or completely free of processing aids. Examples of processing aids include defoamers such as emulsions and / or dispersions of mineral, paraffin, or vegetable oils, dispersions of polydimethylsiloxane (PDMS) fluids, and dispersions of silica hydrophobized with polydimethylsiloxane or other materials. Further processing aids may include particles composed of amide waxes such as ethylene bis-stearamide (EBS) or hydrophobized silica. Further processing aids that can be utilized in the binder composition are surfactants. One or more surfactants may be included in the binder composition to assist in atomization, wetting, and interfacial adhesion of the binder.

[0025] The surfactant is not particularly limited and includes, but is not limited to, ionic surfactants (e.g., sulfates, sulfonates, phosphates, and carboxylates), sulfates (e.g., alkyl sulfates, ammonium lauryl sulfate, sodium lauryl sulfate (SDS), alkyl ether sulfates, sodium laureth sulfate, and sodium myreth sulfate), amphoteric surfactants (e.g., alkyl betaines, such as lauryl-betaine), sulfonates (e.g., sodium dioctyl sulfosuccinate, perfluorooctane sulfonate, perfluorobutane sulfonate, and alkylbenzene sulfonate), phosphates (e.g., alkylaryl ether phosphate and alkyl ether phosphate), carboxylates (e.g., alkyl carboxylates, fatty acid salts (soaps), sodium stearate, sodium lauroyl sarcosinate, carboxylate fluorinated surfactants, perfluoronanoate, and perfluorooctanoate), cationic (e.g., alkylamine salts, such as laurylamine acetate), pH-dependent surfactants (primary, secondary, or tertiary amines), permanently charged quaternary ammonium cations (e.g., alkyltrimethylammonium salts, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetylpyridinium chloride, and benzethonium chloride), as well as zwitterionic surfactants, quaternary ammonium salts (e.g., lauryltrimethylammonium chloride and alkylbenzyldimethylammonium chloride), and surfactants such as polyoxyethylene alkylamines.

[0026] Suitable nonionic surfactants that can be used with the binder composition include polyethers (e.g., condensates of ethylene oxide and propylene oxide, including linear and branched alkyl and aralkyl polyethylene glycols and polypropylene glycol ethers and thioethers), alkylphenoxypoly(ethyleneoxy)ethanol having an alkyl group containing 7 to 18 carbon atoms and 4 to 240 ethyleneoxy units (e.g., heptylphenoxypoly(ethyleneoxy)ethanol and nonylphenoxypoly(ethyleneoxy)ethanol), polyoxyalkylene derivatives of hexitols including sorbitan, sorbide, mannitol, and mannite, partial long-chain fatty acid esters (e.g., polyoxyalkylene derivatives of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, and sorbitan trioleate), condensates of ethylene oxide and a hydrophobic base, where the base is formed by condensing propylene oxide and propylene glycol, sulfur-containing condensates (e.g., condensates prepared by condensing ethylene oxide with a higher alkyl mercaptan such as nonyl, dodecyl, or tetradecyl mercaptan or alkylthiophenol, where the alkyl group contains 6 to 15 carbon atoms), ethylene oxide derivatives of long-chain carboxylic acids (e.g., lauric acid, myristic acid, palmitic acid, and oleic acid, such as tall oil fatty acid), ethylene oxide derivatives of long-chain alcohols (e.g., octyl, decyl, lauryl, or cetyl alcohol), and ethylene oxide / propylene oxide copolymers are included.

[0027] In at least one exemplary embodiment, the surfactant includes one or more of Dynol 607, which is 2,5,8,11 - tetramethyl - 6 - dodecyne - 5,8 - diol; SURFONYL® 420, SURFONYL® 440, and SURFONYL® 465 (commercially available from Evonik Corporation (Allentown, Pa.)), which are ethoxylated 2,4,7,9 - tetramethyl - 5 - decyne - 4,7 - diol surfactants; Stanfax (sodium lauryl sulfate); Surfynol 465 (ethoxylated 2,4,7,9 - tetramethyl 5 - decyne - 4,7 - diol); Triton™ GR - PG70 (sodium 1,4 - bis(2 - ethylhexyl)sulfosuccinate); and Triton™ CF - 10 (poly(oxy - 1,2 - ethanediyl), alpha - (phenylmethyl)-omega-(1,1,3,3 - tetramethylbutyl)phenoxy). The surfactant may be present in the binder composition in an amount of 0 to 10% by weight, 0.1% to 5.0% by weight, or 0.3% to 2.0% by weight, or 0.5% to 1.0% by weight based on the total solids content of the binder composition.

[0028] The binder composition may also contain organic and / or inorganic acids and bases in an amount sufficient to adjust the pH to a desired level as a pH adjuster. The pH can be adjusted based on the intended use so as to facilitate the compatibility of the raw materials of the binder composition or to act on various types of fibers. In some exemplary embodiments, a pH adjuster is utilized to adjust the pH of the binder composition to an acidic pH. Examples of suitable acidic pH adjusters include inorganic acids such as, but not limited to, sulfuric acid, phosphoric acid, and boric acid, and further organic acids such as p-toluenesulfonic acid, mono- or polycarboxylic acids such as, but not limited to, citric acid, acetic acid and their anhydrides, adipic acid, oxalic acid, and their corresponding salts. Also included are inorganic salts that can be acid precursors. The acid adjusts the pH and, in some cases, acts as a crosslinking agent as discussed above. In other exemplary embodiments, organic and / or inorganic bases may be included to raise the pH of the binder composition. In some exemplary embodiments, the base may be a volatile base or a non-volatile base. Exemplary volatile bases include, for example, ammonia and alkyl-substituted amines such as methylamine, ethylamine or 1-aminopropane, dimethylamine, and ethylmethylamine. Exemplary non-volatile bases include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, and t-butylammonium hydroxide.

[0029] The pH adjuster may be present in the binder composition in an amount of 0 to 10% by mass, 0.1% to 5.0% by mass, or 0.3% to 2.0% by mass, or 0.5% to 1.0% by mass based on the total solids content in the binder composition. In some exemplary embodiments, the aqueous binder composition substantially or completely contains no pH adjuster. In the state before curing, the pH of the binder composition can range from 2 to 5, including all amounts and ranges therebetween. In some exemplary embodiments, the pH of the binder composition is from 2.2 to 4.0, such as from 2.5 to 3.8 and from 2.6 to 3.5, in the state before curing. After curing, the pH of the binder composition can increase to at least pH 6.0, such as to a level of 6.5 to 7.2, or 6.8 to 7.2.

[0030] The binder may include a dust suppressant to reduce or eliminate the presence of inorganic and / or organic particles that may adversely affect the subsequent assembly and installation of the insulation material. The dust suppressant can be any conventional mineral oil, mineral oil emulsion, natural or synthetic oil, bio-based oil, or lubricating oil, such as, but not limited to, silicone and silicone emulsions, polyethylene glycol, and any petroleum-based or non-petroleum-based oil with a high flash point so as to minimize the evaporation of the oil in the oven. In some exemplary embodiments, the aqueous binder composition includes up to 10 wt%, such as up to 8 wt%, or up to 6 wt% of the dust suppressant. In various exemplary embodiments, the aqueous binder composition includes from 0 wt% to 10 wt%, such as from 1.0 wt% to 7.0 wt%, or from 1.5 wt% to 6.5 wt%, or from 2.0 wt% to 6.0 wt%, or from 2.5 wt% to 5.8 wt% of the dust suppressant.

[0031] The binder further includes water for dissolving or dispersing the active solids and applying them to the reinforcing fibers. The water may be added in an amount sufficient to dilute the aqueous binder composition to a viscosity suitable for applying it to the reinforcing fibers and further achieving the desired solids content in the fibers. It has been discovered that the binder composition of the present invention can contain a lower solids content than conventional phenol-urea-formaldehyde or carbohydrate-based binder compositions. In particular, the binder composition can contain 3% to 35% by weight of binder solids, for example, without limitation, 10% to 30% by weight, 12% to 20% by weight, and 15% to 19% by weight of binder solids. From this level of solids, it is shown that the binder composition of the present invention can contain more water than traditional binder compositions. However, since the binder composition has a fast curing rate, the binder can be processed at a high gradient moisture level (3% to 30%), and the binder composition requires a shorter curing residence time for moisture removal than traditional binder compositions. The binder content of the product can be measured as loss on ignition (LOI). In certain embodiments, the LOI for glass fibers forming a thermal insulation product is 0.5% to 50%, for example, without limitation, 1% to 25%, 5% to 19%, and 4.5% to 17%. In some exemplary embodiments, the binder composition is capable of achieving the same or higher performance as conventional phenol or starch hybrid binder compositions with a lower LOI.

[0032] In some exemplary embodiments, the aqueous binder composition may also include one or more additives, such as coupling agents, extenders, crosslink density enhancers, deodorants, antioxidants, dust suppressants, biocides, moisture-proof agents, or combinations thereof. The binder may include, without limitation, dyes, pigments, additional fillers, colorants, UV stabilizers, heat stabilizers, anti-foaming agents, emulsifiers, preservatives (e.g., sodium benzoate), corrosion inhibitors, and mixtures thereof. Other additives may be added to the binder composition to improve the performance of the process and the product. Such additives include lubricants, wetting agents, antistatic agents, and / or water repellents. The additives may be present in the binder composition in amounts ranging from trace amounts (e.g., less than 0.1 wt% of the binder composition) to 10 wt% of the total solids of the binder composition. In some exemplary embodiments, the aqueous binder composition is substantially free of monomeric carboxylic acid components. Exemplary monomeric polycarboxylic acid components include aconitic acid, adipic acid, azelaic acid, butanetetracarboxylic acid dihydrate, butanetricarboxylic acid, chlorendic anhydride, citraconic acid, citric acid, dicyclopentadiene-maleic acid adduct, diethylenetriaminepentaacetic acid pentasodium salt, dipentene and maleic anhydride adduct, endomethylenetetrachlorophthalic anhydride, ethylenediaminetetraacetic acid (EDTA), fully maleated rosin, maleated tall oil fatty acid, fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleated rosin oxidized with potassium peroxide following alcohol and then carboxylic acid, malic acid, maleic anhydride, mesaconic acid, oxalic acid, phthalic anhydride, polylactic acid, sebacic acid, succinic acid, tartaric acid, terephthalic acid, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and trimesic acid. In various exemplary embodiments, the aqueous binder composition includes a long-chain polyol (e.g., fully or partially hydrolyzed polyvinyl alcohol), a primary crosslinking agent (e.g., polymeric polycarboxylic acid), and a secondary crosslinking agent (e.g., sugar alcohol). Table 1 shows the range of components used in the binder composition of the present invention according to certain exemplary embodiments.

[0033]

Table 1

[0034] The aqueous binder compositions according to various exemplary embodiments of the present disclosure may further include a catalyst / accelerator (e.g., sodium hypophosphite), a surfactant, and / or a coupling agent (e.g., silane) as shown in Table 2.

Table 2

[0035] In some exemplary embodiments, the binder composition is formulated such that the level of water-soluble substances after curing is reduced, as determined by extracting water-soluble substances with deionized water at room temperature for 2 hours using 1000 g of deionized water per 1 g of the binder. The higher the level of water-soluble substances after curing, the higher the likelihood of leaching when the cured material is exposed to water and / or a high-temperature / high-humidity environment. In some exemplary embodiments, the binder composition has 6% by mass or less of water-soluble substances after curing. In some exemplary embodiments, the binder composition has less than 5.0% by mass, e.g., 5.0% by mass, 4.0% by mass, less than 3.0% by mass, less than 2.5% by mass, less than 2.0% by mass, less than 1.5% by mass, or less than 1.0% by mass of water-soluble substances after curing. It has been found that by reducing the level of water-soluble substances after curing to 6.0% by mass or less, the tensile strength of the binder composition is improved compared to a binder composition having more than 6.0% by mass of water-soluble substances after curing but otherwise similar.

[0036] The amount of water-soluble substances remaining in the binder composition after curing can be determined at least in part by the amount of carboxylic acid groups in the binder. In particular, when the acid groups are in excess, the water-soluble content increases and the water-soluble substances after curing increase. As shown in Table 3 below, Comparative Examples 1 and 2 have a very acidic COOH / OH ratio, and as a result, the percentage of water-soluble substances after curing is unacceptably high. In contrast, the percentage of water-soluble substances remaining after curing substantially decreases at a COOH / OH ratio of 1 / 0.1 or less.

[0037] [Table 3] TIFF0007705690000006.tif128129

[0038] To produce a binder composition with a water-soluble substance level after curing that is acceptably low (e.g., 6% by mass or less), it has further been found that at least 10% by mass of one or more short-chain polyols should be included in the total polyol content. Generally, short-chain polyols such as sorbitol have high water solubility, so this is particularly surprising. Therefore, it was expected that increasing the sorbitol level would increase, rather than decrease, the amount of water-soluble substances in the binder composition.

[0039] In some exemplary embodiments, the binder composition has a viscosity of less than 400 cP at a solids content of 30% or less, for example, 300 cP at a solids content of 30% or less, 200 cP at a solids content of 30% or less, 175 cP at a solids content of 30% or less, 150 cP at a solids content of 30% or less. In various exemplary embodiments, the viscosity of the binder composition is 250 cP or less at a solids content of 30% or less.

[0040] The textile products of the present disclosure include a plurality of randomly oriented fibers. In certain exemplary embodiments, the plurality of randomly oriented fibers are mineral fibers, such as, but not limited to, glass fibers, glass wool fibers, mineral wool fibers, slag wool fibers, stone wool fibers, ceramic fibers, metal fibers, and combinations thereof.

[0041] Other reinforcing fibers, such as natural fibers and / or synthetic fibers, such as carbon, polyester, polyethylene, polyethylene terephthalate, polypropylene, polyamide, aramid, and / or polyaramid fibers, may be used in the nonwoven fiber mat. As used herein, the term "natural fiber" refers to any part of a plant, such as, but not limited to, plant fibers extracted from stems, seeds, leaves, roots, or rhizomes. Examples of natural fibers suitable for use as reinforcing fiber materials include wood fibers, cellulose fibers, straw, wood chips, wood strands, cotton, jute, bamboo, ramie, bagasse, hemp, coir, linen, kenaf, sisal, flax, henequen, and mixtures thereof. The fibrous insulation products may be formed entirely of one type of fiber or a combination of multiple types of fibers. For example, the insulation products may be formed of various combinations of different types of glass fibers, or various combinations of different inorganic fibers and / or natural fibers, depending on the desired application. In certain exemplary embodiments, the insulation products are formed entirely of glass fibers. The present invention has been described generally, and can be further understood by reference to certain specific examples set forth below, which are provided for illustrative purposes only and are not intended to be all-inclusive or limiting unless otherwise specified.

Examples

[0042] (Example 1) Using a binder formulation in which the carboxylic acid / hydroxyl ratio varies and the polyvinyl alcohol / sorbitol ratio varies, thin sheets (curing temperature 425°F and thickness 0.125 inches) were formed and cut into strips. These ratios are shown in Table 4 below. Each sheet strip was subjected to a three-point bend test in which a load was applied at the center of each strip and the amount of load that the sheet strip could withstand until it broke was measured. The results are shown in Figure 1.

[0043]

Table 4

[0044] As shown in Figure 1, within each carboxylic acid / hydroxyl group ratio, the flexural stress / mass / LOI increased or decreased depending on the polyvinyl alcohol / sorbitol ratio. Flexural stress is measured in a three-point bend test using a 2''×6'' sheet with a thickness of 1 / 8'' (i.e., the force until breakage). The highest overall flexural stress / LOI was obtained when the carboxylic acid / hydroxyl group ratio was 1 / 0.66. Furthermore, within this ratio range, the flexural stress / LOI further increased when the polyvinyl alcohol / sorbitol ratio was 0.5 / 0.5. In fact, the highest flexural stress was shown when the polyvinyl alcohol / sorbitol ratio was 0.5 / 0.5 within each set of carboxylic acid / hydroxyl group ratios.

[0045] (Example 2) Using a binder composition in which the COOH / OH ratio and the long-chain polyol / short-chain polyol ratio are varied, a nonwoven fiber glass binder-impregnated filter (BIF) sheet having a width of 9.5 mm, a thickness of 0.5 mm, and a length of 97 mm was formed. The nonwoven fiber glass BIF sheet was cured at 425°F for 3 minutes and 30 seconds. The tensile strength, loss on ignition (LOI), and tensile strength divided by LOI (tensile strength / LOI) of each sample were measured under ambient conditions and steam ("high temperature / high humidity") conditions. The tensile strength was measured using an Instron (tensile rate of 2 inches / min). The LOI of the reinforcing fiber is the mass loss of the fiber after heating the fiber to a temperature sufficient for the binder composition to burn or thermally decompose from the fiber. The LOI was measured according to the procedure shown in TAPPI T-1013 OM06, Loss on Ignition of Fiberglass Mats (2006). To create a high temperature / high humidity environment, the filter sheet was placed in an autoclave at 240°F and a pressure between 400 and 500 psi for 60 minutes. As shown in Figure 2, the tensile / LOI as a whole appeared to increase as the ratio of short-chain polyol in the composition increased (within a COOH / OH ratio of 1 / 0.1) under both ambient conditions and high temperature / high humidity conditions. This relationship appears to coincide with the level of water-soluble substances remaining in the composition after curing (Figure 3). Figure 3 shows that as the ratio of short-chain polyol increases, the percentage of water-soluble substances in the cured composition decreases.

[0046] As shown in Figures 4 and 5, this relationship continued when the COOH / OH ratio was adjusted to 1 / 1.5. However, it should be noted that the percentage of water-soluble substances remaining in the composition after curing decreased substantially within this COOH / OH range. For example, even in a composition without short-chain polyol, the percentage of water-soluble substances was less than 8.0%, and when a certain amount of short-chain polyol was added, the percentage dropped below 5.0%. However, when the COOH / OH ratio was adjusted to 1 / 0.5, 1 / 0.1, and 1 / 1, the percentage of water-soluble substances decreased similarly with the increase in the ratio of short-chain polyol for both, but both the ambient and high-temperature / high-humidity tensile strengths remained relatively constant regardless of the long-chain polyol / short-chain polyol ratio. See FIGS. 6-9. However, it should be noted that the highest ambient tensile strength / LOI was shown at a long-chain polyol / short-chain polyol ratio of 0.5 / 0.5 and 0.3 / 0.7 when the COOH / OH ratio was 1 / 0.5 (tensile strength / LOI of 44 and 45 respectively).

[0047] FIG. 10 shows the change in tensile / LOI of a binder composition-impregnated filter sheet in which the COOH / OH ratio changes from 1 / 0.1 to 1 / 10. As shown, the optimal tensile / LOI under both ambient conditions and high-temperature / high-humidity conditions can be seen when the COOH / OH ratio is neither too low nor too high. At a COOH / OH ratio that is too high or too low, the tensile / LOI under high-temperature / high-humidity conditions deteriorates and the strength properties become insufficient.

[0048] (Example 3) Fiberglass insulation boards (e.g., ceiling tiles) were formed using binder compositions with varying ratios. The insulation boards formed with the binder compositions according to the present application (denoted as PAA / S / PVOH of polyacrylic acid / sorbitol / polyvinyl alcohol with various ratios) were compared with boards formed using both a conventional carbohydrate-based binder composition ("starch hybrid binder board") and a phenol-urea-formaldehyde binder composition ("PUF board"). The elastic modulus, compressive strength (delta b), and sag (inch) of each sample were determined under ambient conditions. As shown in FIG. 11, compared with both the conventional carbohydrate-based binder composition and the phenol-urea-formaldehyde-based binder composition, the PAA / S / PVOH insulation board samples each showed improved flexural modulus. The highest improvement was shown when PAA / S / PVOH was 50:20:30 and when PAA / S / PVOH was 60:10:30, and the flexural modulus levels were 70 psi and 68 psi, respectively. In contrast, the PUF board showed a flexural modulus of 46 psi, and the starch hybrid binder board showed an elastic modulus of 31 psi. In some exemplary embodiments, the insulation board according to the concepts of the present invention, with a thickness of 1 inch and a density of 6 lbs / ft 3 achieves an elastic modulus of at least 40 psi, such as at least 45 psi, at least 50 psi, and at least 55 psi.

[0049] FIG. 12 shows the sag observed in various 4'×4' insulation board panels after being left in a high temperature / high humidity environment of 90°F / 90% rH (relative humidity) for a predetermined number of days. As shown in FIG. 12, PAA / S / PVOH binder compositions with low PVOH levels (i.e., 60:20:15 PAA / S / PVOH and 75:10:15 PAA / S / PVOH) showed less sag under high temperature / high humidity conditions than both the PUF board and the starch hybrid binder board. This indicates that reducing the long-chain polyol in the binder composition may facilitate the improvement of high temperature / high humidity performance in applications where a very high standard of high temperature / high humidity performance is required.

[0050] FIG. 13 shows the compressive strength at 10% deformation of fiber glass board products with different binders and LOI%. The test was conducted on 6''×6'' insulation boards with a thickness of 1'' and a density of 6 lb / ft 2 in accordance with ASTM method C-165. As shown in FIG. 13, the compressive strength of the insulation board formed with the PAA / S / PVOH binder exceeded the compressive strength of the insulation boards formed with both the starch hybrid binder and the PUF binder, at 260 lbs / ft 2~500 lbs / ft 2 Compressive strength exceeding was shown. In some exemplary embodiments, a 6’’×6’’ insulation board with a thickness of 1 inch according to the concept of the present invention has at least 200 lbs / ft 2 , for example at least 300 lbs / ft 2 , at least 400 lbs / ft 2 , and at least 500 lbs / ft 2 of compressive strength is achieved.

[0051] Figure 14 shows the bond strength at break of fiberglass board products with different binders and LOI%. In the test, the strength in the Z direction of a 6’’×6’’ insulation board with a thickness of 1’’ and a density of 6 lb / ft 2 was measured. As shown in Figure 14, the bond strength of the insulation board formed with the PAA / S / PVOH binder exceeded that of the insulation board formed with the starch hybrid binder. Further, the insulation board formed with the PAA / S / PVOH binder showed a bond strength equivalent to that of the insulation board formed with the PUF binder, with a bond strength exceeding 10 lbs / ft 2 ~15 lbs / ft 2 . In some exemplary embodiments, a 6’’×6’’ insulation board with a thickness of 1 inch according to the concept of the present invention has at least 7.5 lbs. / ft 2 / LOI, for example at least 10 lbs. / ft 2 / LOI, at least 12.5 lbs. / ft 2 / LOI, and at least 15 lbs. / ft 2 / LOI of bond strength is achieved.

[0052] (Example 4) Binder compositions containing 75 mass% polyacrylic acid with varying amounts of polyvinyl alcohol and sorbitol (Table 5) or triethanolamine (Table 6) were used to form nonwoven fiber glass binder impregnated filter (BIF) sheets 9.5 mm wide, 0.5 mm thick and 97 mm long. The nonwoven fiber glass BIF sheets were cured in a convection oven at 425°F for 3 minutes 30 seconds. The tensile strength normalized by LOI (tensile strength / LOI) was measured for each sample under ambient conditions and under steam ("high temperature / high humidity") conditions. Tensile strength was measured using an Instron (tensile rate of 2 inches / minute). The LOI of the reinforcing fiber is the mass loss of the fiber after heating the fiber to a temperature sufficient for the binder composition to burn or pyrolyze from the fiber. LOI was measured according to the procedure described in TAPPI T-1013 OM06, Loss on Ignition of Fiberglass Mats (2006). To create a high temperature / high humidity environment, the filter sheets were placed in an autoclave at 227°F and 5 psi for 60 minutes. The binder compositions tested are detailed in Table 5 below.

[0053]

Table 5

[0054]

Table 6

[0055] As shown in Table 5, a filter sheet formed of a binder composition containing polyacrylic acid and 25% by mass of sorbitol shows an increase in both ambient conditions and high temperature / high humidity in terms of tensile strength / LOI when a small amount (1.0% to 20% by mass) of polyvinyl alcohol is included (see Examples 1-4 and Comparative Example A). Similarly, as shown in Table 6, a filter sheet formed of a binder composition containing polyacrylic acid and 25% by mass of triethanolamine shows an increase in both ambient conditions and high temperature / high humidity in terms of tensile strength / LOI when a small amount (1.0% to 20% by mass) of polyvinyl alcohol is included (see Examples 10-13 and Comparative Example C). The results of this test are described in Example 15.

[0056] Furthermore, a filter sheet formed of a binder composition containing polyacrylic acid and 20% by mass of polyvinyl alcohol shows an increase in ambient condition tensile strength / LOI when either a small amount (1.0% to 20% by mass) of sorbitol or triethanolamine is included (see Examples 5-8 vs. Comparative Example B and Examples 14-17 vs. Comparative Example D). A filter sheet formed of a binder composition containing a small amount of sorbitol further showed an increase in tensile strength / LOI under high temperature / high humidity conditions. The results of this test are described in Figure 16. Furthermore, adding a small amount of triethanolamine to a composition containing 20% by mass of PVOH did not significantly affect the tensile strength / LOI under high temperature / high humidity conditions. Each of Examples 14-17 showed improved tensile / LOI compared to a sheet formed using a binder composition excluding PVOH.

[0057] Furthermore, as described with reference to FIGS. 17 and 18, surprisingly, the addition of a small amount of PVOH decreased the viscosity of the binder composition. FIG. 17 illustrates the viscosity profiles for binder compositions containing 75 wt % polyacrylic acid with varying concentrations of triethanolamine and polyvinyl alcohol. As described, a composition containing 75 wt % polyacrylic acid and 25 wt % triethanolamine exhibits a viscosity profile between 160 and 310 cP over a temperature range of 50°F to 90°F. In contrast, the addition of a small amount of PVOH, 1.0 or 2.5 wt %, decreases the viscosity profile to between 30 and 75 cP over the same temperature range.

[0058] Most of the more detailed aspects of the exemplified products and processes are known in the art, and such aspects are omitted for the purpose of presenting accurately the general concept of the present invention. While the present invention has been described with reference to specific means, materials and embodiments, from the foregoing, one skilled in the art can readily ascertain the essential characteristics of this disclosure and make various changes and modifications to adapt it to various usages and characteristics without departing from the spirit and scope of the invention as set forth above and as shown in the appended claims. Another aspect of the present invention may be as follows. 〔1〕An aqueous binder composition, a crosslinking agent containing at least 35% by mass of at least two carboxylic acid groups based on the total solid content of the aqueous binder composition; and at least 0.1 to 50.0% by mass of at least two hydroxyl groups and a number average molecular weight of at least 2,000 daltons based on the total solid content of the aqueous binder composition. containing at least one long-chain polyol having; It may contain at least one short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 daltons; An aqueous binder composition that contains 6.0% by mass or less of water-soluble substances when cured. 〔2〕The aqueous binder composition according to 〔1〕 above, wherein the short-chain polyol is present in an amount of 1.0 to 50% by mass based on the total solid content of the aqueous binder composition. 〔3〕The aqueous binder composition according to 〔1〕 above, wherein the short-chain polyol is present in an amount of 10.0 to 25% by mass based on the total solid content of the aqueous binder composition. 〔4〕The aqueous binder composition according to 〔1〕 above, wherein the short-chain polyol contains one or more of sugar alcohol, 2,2-bis(methylol)propionic acid, tri(methylol)propane, pentaerythritol, and alkanolamine. 〔5〕The aqueous binder composition according to 〔4〕 above, wherein the short-chain polyol contains a sugar alcohol selected from the group consisting of glycerol, erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, iditol, isomaltitol, lactitol, cellobiitol, palatinitol, maltotritol, their syrups, and their mixtures. 〔6〕The aqueous binder composition according to 〔4〕 above, wherein the alkanolamine contains triethanolamine. 〔7〕The aqueous binder composition according to 〔1〕 above, wherein the ratio of the long-chain polyol to the short-chain polyol is between 1 / 50 and 20 / 1. 〔8〕The aqueous binder composition according to 〔1〕 above, wherein the ratio of the long-chain polyol to the short-chain polyol is between 1 / 20 and 10 / 1. 〔9〕The aqueous binder composition according to 〔1〕, which contains 5.0% by mass or less of a water-soluble substance when cured. 〔10〕The aqueous binder composition according to 〔1〕, which contains 4.0% by mass or less of a water-soluble substance when cured. 〔11〕The aqueous binder composition according to 〔1〕, having a viscosity of 175 cP at a solid content of 30% or less. 〔12〕The aqueous binder composition according to 〔1〕, which has a pH between 5 and 9.0 when cured. 〔13〕An aqueous binder composition comprising: At least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 daltons, in an amount of 0.1 to 50.0% by mass based on the total solid content of the aqueous binder composition; A crosslinking agent containing at least two carboxylic acid groups, in an amount of at least 35% by mass based on the total solid content of the aqueous binder composition; and At least one short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 daltons, in an amount of 1.0 to 50% by mass, wherein the ratio of the molar equivalent of carboxylic acid groups, anhydride groups or their salts to the molar equivalent of hydroxyl groups is 1 / 0.05 to 1 / 20, and the ratio of the long-chain polyol to the short-chain polyol is between 1 / 50 and 20 / 1. 〔14〕The aqueous binder composition according to 〔13〕, wherein the long-chain polyol is present in an amount of 1.0 to 45% by mass based on the total solid content of the aqueous binder composition. 〔15〕The aqueous binder composition according to 〔13〕, wherein the short-chain polyol is present in an amount of 10.0 to 25% by mass based on the total solid content of the aqueous binder composition. 〔16〕The aqueous binder composition according to 〔13〕, wherein the short-chain polyol contains one or more of sugar alcohols, 2,2-bis(methylol)propionic acid, tri(methylol)propane and alkanolamines. 〔17〕The aqueous binder composition according to 〔16〕, wherein the short-chain polyol contains a sugar alcohol selected from the group consisting of glycerol, erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, iditol, isomaltitol, lactitol, cellobiitol, palatinitol, maltotriitol, their syrups and their mixtures. 〔18〕The aqueous binder composition according to 〔16〕, wherein the alkanolamine contains triethanolamine. 〔19〕The aqueous binder composition according to 〔13〕, wherein the ratio of the long-chain polyol to the short-chain polyol is between 1 / 50 and 20 / 1. 〔20〕The aqueous binder composition according to 〔13〕, wherein the ratio of the long-chain polyol to the short-chain polyol is between 1 / 20 and 10 / 1. 〔21〕The aqueous binder composition according to 〔13〕, which contains 6.0% by mass or less of water-soluble substances when cured. 〔22〕The aqueous binder composition according to 〔13〕, which contains 4.0% by mass or less of water-soluble substances when cured. 〔23〕A fibrous product, a plurality of randomly oriented fibers; and an aqueous binder composition that at least partially coats the fibers, and the binder composition a crosslinking agent containing at least 35% by mass, based on the total solid content of the aqueous binder composition, of at least two carboxylic acid groups; and contains at least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 daltons, in an amount of 0.1 to 50.0% by mass based on the total solid content of the aqueous binder composition; may contain at least one short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 daltons; A fibrous product that contains 6.0% by mass or less of water-soluble substances when cured. 〔24〕The fibrous product according to 〔23〕, which includes any one of a heat insulating material product, a non-woven mat, a particle board, a ceiling board, and a duct board. 〔25〕The fibrous product according to 〔23〕, wherein the short-chain polyol is present in an amount of 1.0 to 45% by mass based on the total solid content of the aqueous binder composition. 〔26〕The fibrous product according to 〔23〕, wherein the short-chain polyol is present in an amount of 10.0 to 25% by mass based on the total solid content of the aqueous binder composition. 〔27〕The fibrous product according to 〔23〕, wherein the short-chain polyol contains one or more of sugar alcohol, 2,2-bis(methylol)propionic acid, tris(methylol)propane, and alkanolamine. 〔28〕The fibrous product according to the above-mentioned 〔23〕, wherein the short-chain polyol contains a sugar alcohol selected from the group consisting of glycerol, erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, iditol, isomaltitol, lactitol, cellobiitol, palatinite, maltotriitol, their syrups and their mixtures. 〔29〕The fibrous product according to the above-mentioned 〔28〕, wherein the alkanolamine contains triethanolamine. 〔30〕The fibrous product according to the above-mentioned 〔23〕, wherein the ratio of the long-chain polyol to the short-chain polyol is between 1 / 50 and 20 / 1. 〔31〕The fibrous product according to the above-mentioned 〔23〕, wherein the ratio of the long-chain polyol to the short-chain polyol is between 1 / 20 and 10 / 1. 〔32〕The fibrous product according to the above-mentioned 〔23〕, wherein when cured, the binder composition contains 5.0% by mass or less of water-soluble substances. 〔33〕The fibrous product according to the above-mentioned 〔23〕, wherein when cured, the binder composition contains 4.0% by mass or less of water-soluble substances.

Claims

1. An aqueous binder composition comprising: A polymeric crosslinking agent containing at least 35% by mass of at least two carboxylic acid groups based on the total solid content of the aqueous binder composition; and at least 0.1 to 50.0% by mass of at least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 daltons based on the total solid content of the aqueous binder composition; the aqueous binder composition does not contain a monomeric carboxylic acid component; It may contain at least one short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 daltons; An aqueous binder composition which, when cured, contains 6.0% by mass or less of water-soluble substances and the ratio of the molar equivalent of carboxylic acid groups, anhydride groups or their salts to the molar equivalent of hydroxyl groups is 1 / 0.5 to 1 / 10.

2. The aqueous binder composition according to claim 1, wherein the short-chain polyol is present in an amount of 1.0 to 50% by mass based on the total solid content of the aqueous binder composition.

3. The aqueous binder composition according to claim 1, wherein the short-chain polyol is present in an amount of 10.0 to 25% by mass based on the total solid content of the aqueous binder composition.

4. The aqueous binder composition according to claim 1, wherein the short-chain polyol contains one or more of sugar alcohols, 2,2-bis(methylol)propionic acid, tri(methylol)propane, pentaerythritol and alkanolamine.

5. The aqueous binder composition according to claim 4, wherein the short-chain polyol contains a sugar alcohol selected from the group consisting of glycerol, erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, iditol, isomaltitol, lactitol, cellobiitol, palatinite, maltotriitol, their syrups and their mixtures.

6. The aqueous binder composition according to claim 4, wherein the alkanolamine contains triethanolamine.

7. The aqueous binder composition according to claim 1, wherein the molar ratio of the long-chain polyol to the short-chain polyol is between 1 / 50 and 20 / 1.

8. The aqueous binder composition according to claim 1, wherein the molar ratio of the long-chain polyol to the short-chain polyol is between 1 / 20 and 10 / 1.

9. The aqueous binder composition according to claim 1, which contains 5.0% by mass or less of a water-soluble substance when cured.

10. The aqueous binder composition according to claim 1, which contains 4.0% by mass or less of a water-soluble substance when cured.

11. The aqueous binder composition according to claim 1, having a viscosity of 175 cP at a solid content of 30% or less.

12. The aqueous binder composition according to claim 1, which has a pH between 5 and 9.0 when cured.

13. An aqueous binder composition, at least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 daltons, in an amount of 0.1 to 50.0% by mass based on the total solid content of the aqueous binder composition; a polymeric crosslinking agent containing at least 35% by mass of at least two carboxylic acid groups based on the total solid content of the aqueous binder composition; and at least one short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 daltons, in an amount of 1.0 to 50% by mass, the aqueous binder composition not containing a monomeric carboxylic acid component, and the ratio of the molar equivalent of the carboxylic acid group, anhydride group or their salts to the molar equivalent of the hydroxyl group being 1 / 0.5 to 1 / 10, and the molar ratio of the long-chain polyol to the short-chain polyol being between 1 / 50 and 20 / 1.

14. The aqueous binder composition according to claim 13, wherein the long-chain polyol is present in an amount of 1.0 to 45% by mass based on the total solid content of the aqueous binder composition.

15. The aqueous binder composition according to claim 13, wherein the short-chain polyol is present in an amount of 10.0 to 25% by mass based on the total solid content of the aqueous binder composition.

16. The aqueous binder composition according to claim 13, wherein the short-chain polyol contains one or more of sugar alcohol, 2,2-bis(methylol)propionic acid, trimethylolpropane and alkanolamine.

17. The aqueous binder composition according to claim 16, wherein the short-chain polyol contains a sugar alcohol selected from the group consisting of glycerol, erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, iditol, isomaltitol, lactitol, cellobiitol, palatinite, maltotritol, their syrups and their mixtures.

18. The aqueous binder composition according to claim 16, wherein the alkanolamine contains triethanolamine.

19. The aqueous binder composition according to claim 13, wherein the molar ratio of the long-chain polyol to the short-chain polyol is between 1 / 20 and 10 / 1.

20. The aqueous binder composition according to claim 13, which contains 6.0% by mass or less of water-soluble substances when cured.

21. The aqueous binder composition according to claim 13, which contains 4.0% by mass or less of water-soluble substances when cured.

22. A fibrous product, a plurality of randomly oriented fibers; and an aqueous binder composition that at least partially coats the fibers, the binder composition comprising: a polymeric crosslinking agent containing at least 35% by mass, based on the total solid content of the aqueous binder composition, of at least two carboxylic acid groups; and at least 0.1 to 50.0% by mass, based on the total solid content of the aqueous binder composition, of at least one long-chain polyol having at least two hydroxyl groups and a number average molecular weight of at least 2,000 daltons; the aqueous binder composition does not contain a monomeric carboxylic acid component; optionally contains at least one short-chain polyol having at least two hydroxyl groups and a number average molecular weight of less than 2,000 daltons; a fibrous product which, when cured, contains 6.0% by mass or less of water-soluble substances and has a ratio of the molar equivalent of carboxylic acid groups, anhydride groups or their salts to the molar equivalent of hydroxyl groups of 1 / 0.5 to 1 / 10.

23. The fibrous product according to claim 22, wherein the binder composition contains 5.0% by mass or less of water-soluble substances when cured.

24. The fibrous product according to claim 22, wherein the binder composition contains 4.0% by mass or less of water-soluble substances when cured.

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