Aqueous binder composition suitable for B-stage formation

Abstract

To provide an aqueous binder composition, etc., comprising a monomer polyol having at least four hydroxyl groups; and a crosslinking agent containing a polymer polycarboxylic acid having at least two carboxylic acid groups. [Solution] An aqueous binder composition is provided, comprising a monomer polyol having at least four hydroxyl groups in an amount of 5.0 to 50.0% by mass relative to the total solids content of the aqueous binder composition, and a crosslinking agent comprising a polymer polycarboxylic acid having at least two carboxylic acid groups in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition, wherein the composition has a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.15 / 1.0 to 2.23 / 1, a pH of 2.2 to 4.0, and a viscosity of 10 cP to 60 cP at 25C with a solids content of 40%.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit and priority of U.S. Provisional Application No. 63 / 086,267, filed on October 1, 2020, the entire content of which is incorporated herein by reference.

Background Art

[0002] Aqueous binder compositions have been conventionally used in the formation of woven and non - woven fiber products such as insulation products, composite products, and wood fiber boards. Insulation products, such as glass fiber and mineral wool insulation products, are typically manufactured by spinning a molten composition of a polymer, glass, or other mineral into extremely fine fibers from a spinning device such as a rotary spinner. To form an insulation product, the fibers produced by the rotary spinner are drawn downward from the spinner towards a conveyor by a blower. As the fibers move downward, a binder material is sprayed onto the fibers, and the fibers are collected on the conveyor into a continuous high - loft blanket. The binder material provides elasticity for restoration after packaging the insulation product, and provides hardness and handleability so that the insulation product can be handled and applied, if necessary, to the insulation cavities of a building. The binder composition also protects the fibers from inter - filament wear and promotes the compatibility between individual fibers. The blanket containing the fibers coated with the binder is then passed through a curing oven, where the binder cures and the blanket is set to the desired thickness. After the binder has cured, the fiber insulation can be cut to a certain length to form individual insulation products, and the insulation products can be packaged for shipment to customer locations.

[0003] The fiberglass insulation products prepared in this manner can be supplied in various forms, including bats, blankets, and boards (heat-compressed bats), for use in different applications. As the binder-coated fiber bats exit the molding chamber, they tend to expand as a result of the elasticity of the glass fibers. The expanded bats are typically transported to and through a curing oven, where heated air is passed through the insulation product to cure the binder. In addition to curing the binder, the insulation product can be compressed with a flight or rollers within the curing oven to give the blanket, bat, or board product the desired dimensions and surface finish. Traditionally, phenol-formaldehyde (PF) binder compositions and PF resins (PUF resins) bulked with urea have been used to manufacture fiberglass insulation products. In insulation boards, also known as "heavyweight" products such as ceiling panels, duct traps, and duct liners, phenol-formaldehyde binder technology has been utilized for producing heavyweight products that are inexpensive and possess acceptable physical and mechanical properties. However, formaldehyde-based binders release undesirable emissions during the manufacturing of fiberglass insulation materials.

[0004] As an alternative to formaldehyde-based binders, specific formaldehyde-free formulations have been developed for use as binders in fiber insulation products. A common manufacturing process for fiber insulation products involves a process step (known as "B-staging") in which an uncured binder-impregnated fiberglass web remains uncured and exposed to ambient conditions for an extended period. Such prolonged exposure causes drying out and surface solidification of the fiber insulation product, resulting in insufficient bond formation between the binder composition and the fibers after curing. The cured finished product exhibits low tensile strength due to the insufficient bond between the fibers and the binder composition. Therefore, there is a need for an environmentally friendly, formaldehyde-free binder composition that exhibits improved shelf life and fiber wetting properties even after prolonged exposure to ambient conditions. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] U.S. Patent Application Publication No. 2019 / 0106564 [Overview of the project]

[0006] Various exemplary embodiments of the concept of the present invention relate to an aqueous binder composition comprising a crosslinking agent comprising a monomer polyol having at least four hydroxyl groups in an amount of 5.0 to 50.0% by mass relative to the total solids content of the aqueous binder composition, and a polymer polycarboxylic acid having at least two carboxylic acid groups in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition, wherein the ratio of molar equivalents of carboxylic acid groups to hydroxyl groups is 0.15 / 1.0 to 2.23 / 1, or 0.26 / 1.0 to 0.75 / 1. In any of the exemplary embodiments, the aqueous binder composition has a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.60 / 1.0 to 1.0 / 0.6. The aqueous binder composition has a pH of 2.2 to 4.0, a solids content of 40%, and a viscosity of 10 cP to 60 cP at 25°C. In any of the exemplary embodiments, the crosslinking agent may include polyacrylic acid. The crosslinking agent may be present in the binder composition in an amount of 52.0 to 72% by mass relative to the total solids content of the aqueous binder composition. In any of the exemplary embodiments, the monomer polyol may contain at least five hydroxyl groups. The monomer polyol may contain one or more of the following: sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, short-chain alkanolamines, and mixtures thereof. In other exemplary embodiments, the monomer polyol is selected from the group consisting of pentaerythritol, xylitol, sorbitol, and mixtures thereof. In any of the exemplary embodiments, the monomer polyol is present in the binder composition in an amount of 15 to 37% by mass relative to the total solids content of the aqueous binder composition. In any of the exemplary embodiments, the composition may not contain a polymer polyhydroxy compound. In any of the exemplary embodiments, the composition may not contain monomeric carboxylic acids. In any of the exemplary embodiments, the aqueous binder composition may have a solids content of 40% and a viscosity of 25 cP to less than 60 cP at 25°C.

[0007] A further embodiment of the concept of the present invention relates to a fibrous thermal insulation product comprising a plurality of randomly oriented fibers and a crosslinked formaldehyde-free binder composition that at least partially coats the fibers. The crosslinked formaldehyde-free binder composition is formed from an aqueous binder composition comprising a crosslinking agent containing less than 5.5% by mass of a water-soluble material and at least one monomer polyol having at least four hydroxyl groups in an amount of 5.0 to 50.0% by mass relative to the total solids content of the aqueous binder composition; and a polymer polycarboxylic acid having at least two carboxylic acid groups in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. The aqueous binder composition has a pH of 2.2 to 4.0 and a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.15 / 1.0 to 2.23 / 1, or 0.26 / 1.0 to 0.75 / 1. In any of the exemplary embodiments, the aqueous binder composition has a molar equivalent ratio of carboxylic acid groups to hydroxyl groups, which may be 0.60 / 1.0 to 1.0 / 0.6.

[0008] The fibers may include one or more of mineral fibers, natural fibers, and synthetic fibers. For example, the fibers may include glass fibers, mineral wool fibers, or mixtures thereof. In any of the exemplary embodiments, the binder composition may not contain a polymer polyhydroxy compound. In any of the exemplary embodiments, the ratio of the molar equivalents of the carboxylic acid group to the hydroxyl group may be 0.80 / 1.0 to 1.0 / 0.8. In any of the exemplary embodiments, the monomer polyol may include one or more of sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, short-chain alkanolamines, and mixtures thereof.

[0009] A further embodiment of the concept of the present invention relates to a B-stageable fibrous insulation product comprising a plurality of randomly oriented fibers; and an uncured aqueous binder composition that at least partially coats the fibers. The aqueous binder composition comprises a crosslinking agent comprising at least one monomer polyol having at least four hydroxyl groups in an amount of 5.0 to 37.0% by mass relative to the total solids content of the aqueous binder composition, and a polymer polycarboxylic acid having at least two carboxylic acid groups in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. The uncured aqueous binder composition has a solids content of 40% and a viscosity of 10 cP to 60 cP at 25°C. Furthermore, the B-stageable fibrous insulation product has a drying time of at least 500 seconds as measured by a CEM Smart 6 moisture analyzer.

[0010] In any of the exemplary embodiments, the uncured aqueous binder composition may have a solids content of 40% and a viscosity of 30 cP to 45 cP at 25°C. In any of the exemplary embodiments, the crosslinking agent may be a homopolymer or copolymer of acrylic acid, such as polyacrylic acid. In any of the exemplary embodiments, the aqueous binder composition may have a pH of 2.2 to 4.0. In any of the exemplary embodiments, the aqueous binder composition may have a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.15 / 1.0 to 2.23 / 1 or 0.26 / 1.0 to 0.75 / 1. In any of the exemplary embodiments, the aqueous binder composition may have a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.60 / 1.0 to 1.0 / 0.6. In any of the exemplary embodiments, the monomer polyol comprises one or more of the following: sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, short-chain alkanolamines, and mixtures thereof. In any of the exemplary embodiments, the composition does not contain a polymer polyhydroxy compound. In any of the exemplary embodiments, the composition does not contain a monomeric carboxylic acid.

[0011] A further embodiment of the concept of the present invention relates to a method for producing a fiber insulation product having a low level of water-soluble material, comprising the step of applying a formaldehyde-free binder composition to a plurality of fibers. The formaldehyde-free binder composition comprises a crosslinking agent comprising at least one monomer polyol having at least four hydroxyl groups in an amount of 5.0 to 50.0% by mass relative to the total solids content of the aqueous binder composition; and a polymer polycarboxylic acid having at least two carboxylic acid groups in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. The method further comprises the steps of gathering the fibers onto a substrate to form a binder-filled fiber pack; and curing the binder-filled fiber pack, wherein the fiber insulation product contains less than 5.5% by mass of water-soluble material.

[0012] In any of the exemplary embodiments, the formaldehyde-free binder composition may contain a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.15 / 1.0 to 2.23 / 1 or 0.26 / 1.0 to 0.75 / 1. In any of the exemplary embodiments, the aqueous binder composition may have a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.60 / 1.0 to 1.0 / 0.6. In any of the exemplary embodiments, the formaldehyde-free binder composition may have a pH of 2.2 to 4.0. In any of the exemplary embodiments, the formaldehyde-free binder composition may have a solid content of 40% and a viscosity of 10 cP to 60 cP at 25°C.

[0013] A further embodiment of the concept of the present invention relates to a method for B-staging a fiber insulation precursor, comprising the steps of: applying a formaldehyde-free binder composition to a plurality of fibers to form a binder-impregnated fiber insulation precursor; exposing the binder-impregnated fiber insulation precursor to ambient temperature for at least 500 seconds to form a B-staged fiber precursor without the binder composition forming a film on the surface of the fiber insulation precursor. The binder composition comprises a crosslinking agent comprising 5.0 to 50.0% by mass of at least one monomer polyol having at least four hydroxyl groups, based on the total solids content of the aqueous binder composition; and at least 50.0% by mass of a polymer polycarboxylic acid having at least two carboxylic acid groups, based on the total solids content of the aqueous binder composition.

[0014] Another further embodiment of the concept of the present invention relates to an aqueous formaldehyde-free binder composition comprising at least one monomer polyol having at least four hydroxyl groups, in an amount of 5.0 to 37.0% by mass based on the total solids content of the aqueous binder composition, 50.0 to 62% by mass of a polyacrylic acid crosslinking agent; 0.5 to 5.0% by mass of a catalyst; 2.0 to 15.0% by mass of a processing aid; 0 to 5.0% by mass of a surfactant; 0 to 2.0% by mass of a pigment; and 0 to 15% by mass of silicone. The aqueous binder composition comprises a molar equivalent ratio of carboxylic acid groups to hydroxyl groups that is 0.15 / 1.0 to 2.23 / 1 or 0.26 / 1.0 to 0.75 / 1. In any of the exemplary embodiments, the aqueous binder composition may have a molar equivalent ratio of carboxylic acid groups to hydroxyl groups that is 0.60 / 1.0 to 1.0 / 0.6. The aqueous binder composition has a pH of 2.2 to 4.0, as well as a solids content of 40% and a viscosity of 30 cP to 55 cP at 25°C. Many other aspects, advantages and / or features of the general concept of the present invention will become more readily apparent from the following detailed description of the exemplary embodiments and the accompanying drawings submitted herewith.

[0015] The general concept of the present invention, as well as its exemplary embodiments and advantages, are described in more detail below by way of example with reference to the drawings.

Brief Description of the Drawings

[0016] [Figure 1] The mass percentage of extractable solids based on the cured binder composition is shown graphically. [Figure 2] The drying times of various binder compositions measured by a CEM Smart 6 moisture balance are shown graphically. [Figure 3] The mass loss (in grams) of a glass fiber roll measured at 25°C at periodic time intervals with a humidity of 46% is shown graphically. [Figure 4] The mass loss (in grams) of a binder-impregnated glass fiber roll measured at 25°C at periodic time intervals with a humidity of 75% is shown graphically. [Figure 5] It shows the mass reduction of the binder-impregnated glass fiber roll measured after 10 minutes at 25 °C with a humidity of 46%, a humidity of 74%, and a humidity of 75%.

Best Mode for Carrying Out the Invention

[0017] 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 these exemplary embodiments belong. The terms used in the description herein are for the purpose of describing exemplary embodiments only and are not intended to limit the exemplary embodiments. Thus, the general concept of the present invention is not intended to be limited to the specific embodiments illustrated herein. Other methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, but 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. "Substantially free of" means that a composition contains less than 1.0% by weight of the listed components, including 0.8% by weight or less, 0.6% by weight or less, 0.4% by weight or less, 0.2% by weight or less, 0.1% by weight or less, and 0.05% by weight or less. In any of the exemplary embodiments, "substantially free of" means that a composition contains 0.01% by weight or less of the listed component.

[0018] Unless otherwise indicated, all numbers expressing amounts of components, chemical and molecular properties, reaction conditions, etc. used in this specification and the claims are to be understood as being modified in all instances by the term "about." Thus, unless the contrary is 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. At the very least, each numerical parameter should be construed in light of the number of significant figures and the ordinary rounding techniques. Unless otherwise indicated, any element, property, feature, or combination of elements, properties and features may be used in any embodiment disclosed herein, regardless of whether the element, property, feature, or combination of elements, properties and features is expressly disclosed in an embodiment. It will be readily understood that a feature described in relation to any particular embodiment described herein may be applicable to other embodiments described herein, provided that the feature is compatible with that embodiment. In particular, a feature described herein in relation to a method may be applicable to a textile product and vice versa; a feature described herein in relation to a method may be applicable to an aqueous binder composition and vice versa; a feature described herein in relation to a textile product may be applicable to an aqueous binder composition and vice versa.

[0019] Although the numerical ranges and parameters representing a broad range of exemplary embodiments are approximations, the numerical values ​​shown in specific embodiments are reported as accurately as possible. However, each numerical value inherently includes certain errors that inevitably arise from the standard deviation found in each test measurement. All numerical ranges given throughout this specification and the claims include all such more precise numerical ranges that fall within such broad numerical ranges, as all more precise numerical ranges are explicitly stated herein. This disclosure relates to formaldehyde-free or "formaldehyde-free" aqueous binder compositions for use with inorganic fibers such as glass or mineral wool fibers. As used herein, the terms “binder composition,” “aqueous binder composition,” “binder formulation,” “binder,” and “binder system” are interchangeable and synonymous. Furthermore, as used herein, the terms “formaldehyde-free” or “formaldehyde-free” are interchangeable and synonymous.

[0020] This disclosure relates to a formaldehyde-free binder composition for use in the manufacture of thermal insulation products having mechanical and physical performance equivalent to or improved compared to products manufactured using conventional formaldehyde-based binder compositions. The formaldehyde-free binder composition can be used in the manufacture of fiber insulation products and related products (hereinafter collectively referred to as fiber insulation products), such as thin fiber-reinforced mats, and glass fiber or mineral wool products, in particular glass fiber or mineral wool insulation products, which are made using a cured formaldehyde-free binder. Other products may include “heavy” products such as composite products, wood fiberboard products, metal building insulation, pipe insulation, ceiling boards, ceiling tiles, e.g., ceiling boards, duct boards, foundation boards, pipe and tank insulation, sound-absorbing boards, acoustic panels, general board products, and board products including duct liners, as well as “light” products such as residential insulation, duct traps, metal building insulation, and flexible duct media. Further fiber products include nonwoven fiber mats and particleboard, and composite products manufactured therefrom. The concept of the present invention is based on the remarkable discovery of an improved formaldehyde-free binder composition comprising a polycarboxylic acid-based crosslinking agent and at least one polyol containing at least three hydroxyl groups or at least four hydroxyl groups. The binder composition of the subject exhibits an unexpected increase in crosslinking density, resulting in unique performance properties including a reduced level of water-soluble material after curing, high water retention, and improved water / steam resistance.

[0021] Non-limiting examples of suitable crosslinking agents include monomers and polymer polycarboxylic acids, which include polycarboxylic acid-based materials having one or more carboxylic acid groups (-COOH), e.g., salts or anhydrides thereof and mixtures thereof. In any of the exemplary embodiments, the polycarboxylic acid may be a polymer polycarboxylic acid, such as a homopolymer or copolymer of acrylic acid. The polymer polycarboxylic acid may include polyacrylic acid (including its salts or anhydrides), and polyacrylic acid resins such as QR-1629S and Acumer 9932, both commercially available from The Dow Chemical Company, polyacrylic acid compositions commercially available from CH Polymer, and polyacrylic acid compositions commercially available from Coatex. Acumer 9932 is a polyacrylic acid / sodium hypophosphite resin with a molecular weight of about 4000 and a sodium hypophosphite content of 6-7% by mass relative to the total mass of the polyacrylic acid / sodium hypophosphite resin. QR-1629S is a polyacrylic acid / glycerin resin composition.

[0022] In some cases, the crosslinking agent may be pre-neutralized with a neutralizing agent. Such a neutralizing agent may include organic and / or inorganic bases, such as sodium hydroxide, ammonium hydroxide, and diethylamine, as well as any type of primary, secondary, or tertiary amine (including alkanolamines). In any of the embodiments disclosed herein, the neutralizing agent may include at least one of sodium hydroxide and triethanolamine. The crosslinking agent is present in the aqueous binder composition in an amount of at least 25.0% by mass relative to the total solids content of the aqueous binder composition, and is not limited to at least 30% by mass, at least 40% by mass, at least 45% by mass, at least 50% by mass, at least 52.0% by mass, at least 54.0% by mass, at least 56.0% by mass, at least 58.0% by mass, and at least 60% by mass. In any of the embodiments disclosed herein, the crosslinking agent is present in the aqueous binder composition in an amount of 27 to 85% by mass relative to the total solids content of the aqueous binder composition, and is not limited to at least 30 to 80% by mass, 50.0 to 70.0% by mass, greater than 50 to 65% by mass, 52.0 to 62.0% by mass, 54.0 to 60.0% by mass, and 55.0 to 59.0% by mass.

[0023] The aqueous binder composition further comprises a polyol containing at least three hydroxyl groups. The polyol may also include water-soluble compounds having a molecular weight of less than 2,000 daltons, including less than 750 daltons, less than 500 daltons, less than 250 daltons, less than 200 daltons, or less than 175 daltons. In any of the embodiments disclosed herein, the polyol may also include a monomeric polyol. Suitable polyol components include sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, and short-chain alkanolamines such as triethanolamine containing at least three hydroxyl groups. In any of the embodiments disclosed herein, the polyol may contain at least four hydroxyl groups, or at least five hydroxyl groups.

[0024] Sugar alcohols are understood to mean compounds obtained when the aldo or keto group of a sugar is reduced to the corresponding hydroxyl group (e.g., by hydrogenation). Starting sugars can be selected from monosaccharides, oligosaccharides, and polysaccharides, as well as mixtures of their products, e.g., syrups, molasses, and starch hydrolysates. The starting sugar may also be a dehydrated form of the sugar. Sugar alcohols closely resemble their corresponding starting sugars, but they are not sugars. Therefore, for example, sugar alcohols do not have reducing ability and cannot participate in the Maillard reaction typical of reducing sugars. In some exemplary embodiments, sugar alcohols include erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, isoditol, isomaltitol, lactitol, cellobitol, palatinitol, maltotitol, their syrups, and mixtures thereof. In various exemplary embodiments, sugar alcohols are selected from sorbitol, xylitol, their syrups, and mixtures thereof. In any of the exemplary embodiments, the polyol is a dimer or oligomeric condensation product of a sugar alcohol.

[0025] In some exemplary embodiments, the polyol is present in the aqueous binder composition in an amount of total solids of up to about 75% by mass or about 70% by mass, including, but not limited to, a total solids content of up to about 68% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 33% by mass, 30% by mass, 27% by mass, 25% by mass and 20% by mass. In some exemplary embodiments, the polyol is present in the aqueous binder composition in an amount of total solids of 2.0% by mass or about 69% by mass, including, but not limited to, a total solids content of 5.0-60.0% by mass, 8.0-57.0% by mass, 10.0-54.0% by mass, 12.0-52.0% by mass, 15.0-50.0% by mass and 20.0-48.0% by mass. In various exemplary embodiments, the crosslinking agent and polyol are present in amounts such that the ratio of the molar equivalents of carboxylic acid groups, anhydride groups, or salts thereof to the molar equivalents of hydroxyl groups is about 0.07 / 1 to about 2.23 / 1, for example, about 0.17 / 1 to about 1 / 0.6, or about 0.32 / 1 to about 0.92 / 1, or about 0.4 / 1 to about 0.6 / 1. In any of the exemplary embodiments, the aqueous binder composition has a molar equivalent ratio of carboxylic acid groups to hydroxyl groups which may be 0.60 / 1.0 to 1.0 / 0.6, or 0.80 / 1 to 1.0 / 0.80.

[0026] In any of the embodiments disclosed herein, the aqueous binder composition may be free from or substantially free from polyols containing fewer than 3 hydroxyl groups, or polyols containing fewer than 4 hydroxyl groups. In any of the embodiments disclosed herein, the aqueous binder composition may be free from or substantially free from polyols having a number average molecular weight of 2,000 daltons or more, for example, 3,000 to 4,000 daltons. Accordingly, in any of the embodiments disclosed herein, the aqueous binder composition may be free from or substantially free from diols, such as glycols, triols, such as glycerol and triethanolamine, and / or polymer polyhydroxy compounds such as polyvinyl alcohol and polyvinyl acetate, which may be partially or completely hydrolyzed, or mixtures thereof. Polyvinyl alcohol is a known film-forming agent that rapidly releases moisture, resulting in film formation. Short-chain polyols are thought to form films less rapidly, improving the B-stage potential of the product.

[0027] In any of the embodiments disclosed herein, the aqueous binder composition may comprise or consist of a polymer polycarboxylic acid-based crosslinking agent and a monomer polyol having at least four hydroxyl groups, wherein the ratio of carboxylic acid groups to hydroxyl groups (OH) is 0.60 / 1 to 1 / 0.6. Optionally, the aqueous binder composition may also contain a known esterification catalyst as a curing accelerator. The catalyst may include inorganic salts, Lewis acids (i.e., ammonium chloride or boron trifluoride), Brønsted 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). Furthermore, 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, but not limited to these, include 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. Furthermore, 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, or mixtures thereof. Additionally, the catalyst may be a mixture of a phosphorus compound and a fluoroborate compound. Other sodium salts, such as sodium sulfate, sodium nitrate, and sodium carbonate, can also be used as catalysts, or alternatively.

[0028] The catalyst may be present in the aqueous binder composition in an amount up to about 10.0% by mass of the total solids of the binder composition, but is not limited to about 1.0 to about 5.0% by mass, or about 1.5 to about 4.5% by mass, or about 1.7 to about 4.0% by mass, or about 2.0 to about 3.5% by mass. Optionally, 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 about 0.01 to about 5.0% by mass, about 0.01 to about 2.5% by mass, about 0.05 to about 1.5% by mass, or about 0.1 to about 1.0% by mass of the total solids of the binder composition.

[0029] Non-limiting examples of silane coupling agents that can be used in binder compositions may be characterized by alkyl, aryl, amino, epoxy, vinyl, methacryloxy, ureido, isocyanate, and mercapto functional groups. In any embodiment, the silane coupling agent may contain a silane containing one or more nitrogen atoms having one or more functional groups such as amines (primary, secondary, tertiary, and quaternary), aminos, iminos, amides, imides, ureidos, or isocyanates. 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), epoxytrialkoxysilanes (e.g., 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane), methylacryltrialkoxysilanes (e.g., 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane), hydrocarbon trialkoxysilanes, aminotrihydroxysilanes, epoxytrihydroxysilanes, methacryltrihydroxysilanes and / or hydrocarbon trihydroxysilanes. In any of the embodiments disclosed herein, the silane may include aminosilanes such as γ-aminopropyltriethoxysilane.

[0030] The aqueous binder composition may further contain processing aids. The processing aids are not particularly limited insofar as they function to facilitate the processing of fiber formation and orientation. Processing aids may be used to improve the uniformity of the binder application distribution, to reduce the viscosity of the binder, to increase the ramp height after formation, to improve the uniformity of the vertical mass distribution, and / or to accelerate the dewatering of the binder in both the formation and oven curing processes. Processing aids may be present in the binder composition in amounts of 0 to about 10.0% by mass, about 0.1 to about 5.0% by mass, or about 0.3 to about 2.0% by mass, or about 0.4 to 1.5% by mass, or about 0.5 to 1.0% by mass, relative to the total solids content of the binder composition. In some exemplary embodiments, the aqueous binder composition is substantially or completely free of any processing aids.

[0031] Examples of processing aids include defoamers, such as emulsions and / or dispersions of minerals, paraffin, or vegetable oils; polydimethylsiloxane (PDMS) solutions; and dispersions of silica hydrophobized with polydimethylsiloxane or other materials. Further processing aids include particles made from amide waxes such as ethylenebis-stearamide (EBS) or hydrophobized silica. A further processing aid that can be used in the binder composition is surfactants. One or more surfactants may be included in the binder composition to assist in atomization, wetting, and interfacial adhesion of the binder.

[0032] The surfactants are not particularly limited, but include, 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, e.g., lauryl betaine), sulfonates (e.g., sodium dioctyl sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, and alkylbenzenesulfonate), phosphates (e.g., alkylaryl ether phosphates and alkyl ether phosphates), and carboxylates (e.g., alkyl carboxylates, fatty acid salts). The surfactants include (soap), sodium stearate, sodium lauroyl sarcosinate, carboxylate fluorinated surfactants, perfluoronanoates and perfluorooctanoates), cations (e.g., alkylamine salts, e.g., 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 polyoxyethylene alkylamines.

[0033] 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 alkalic polyethylene glycol and polypropylene glycol ethers and thioethers), alkylphenoxypoly(ethyleneoxy)ethanol having an alkyl group containing about 7 to about 18 carbon atoms and about 4 to about 240 ethyleneoxy units (e.g., heptylphenoxypoly(ethyleneoxy)ethanol and nonylphenoxypoly(ethyleneoxy)ethanol), polyoxyalkylene derivatives of hexitol including sorbitan, sorbide, mannitan and mannide, and partial long-chain fatty acid esters (e.g., sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trisulfate). Examples include polyoxyalkylene derivatives of thearates, sorbitan monooleate, and sorbitan trioleate; condensates of ethylene oxide and hydrophobic bases, where the base is formed by the condensation of propylene oxide and propylene glycol; sulfur-containing condensates (for example, condensates prepared by condensing ethylene oxide with higher alkyl mercaptans, such as nonyl, dodecyl, or tetradecyl mercaptans, or alkylthiophenols, where the alkyl group contains about 6 to about 15 carbon atoms); ethylene oxide derivatives of long-chain carboxylic acids (for example, lauric acid, myristic acid, palmitic acid, and oleic acid, such as tall oil fatty acids); ethylene oxide derivatives of long-chain alcohols (for example, octyl, decyl, lauryl, or cetyl alcohols); and copolymers of ethylene oxide / propylene oxide.

[0034] In at least one exemplary embodiment, the surfactant is Dynol 607, which is 2,5,8,11-tetramethyl-6-dodecine-5,8-diol; SURFONYL® 420, SURFONYL® 440 and SURFONYL® 465, which are ethoxylated 2,4,7,9-tetramethyl-5-decine-4,7-diol surfactants (commercially available from Evonik Corporation (Allentown, Pa.)); Stanfax (sodium lauryl sulfate); Surfynol It contains one or more of the following: 465 (ethoxylated 2,4,7,9-tetramethyl 5-decine-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).

[0035] Optionally, the aqueous binder composition may contain a dust suppressant to reduce or eliminate the presence of inorganic and / or organic particles that may adversely affect the subsequent fabrication and installation of the insulating material. The dust suppressant may be any conventional mineral oil, mineral oil emulsion, natural or synthetic oil, bio-based oil, or lubricant, for example, but not limited to, silicones and silicone emulsions, polyethylene glycol, and any petroleum-based or non-petroleum-based oil having a high flash point to minimize oil evaporation in the oven. The aqueous binder composition may contain up to about 15% by mass of a dust suppressant, with a maximum of about 14% by mass or up to about 13% by mass. In any of the embodiments disclosed herein, the aqueous binder composition may contain 1.0 to 15% by mass of a dust suppressant, with a maximum of about 3.0 to about 13.0% by mass or up to about 5.0 to about 12.8% by mass.

[0036] The aqueous binder composition may also optionally contain organic and / or inorganic acids and bases as pH adjusters in amounts sufficient to adjust the pH to a desired level. The pH may be adjusted according to the intended use to promote compatibility between the components of the binder composition or to function with various types of fibers. In some exemplary embodiments, pH adjusters are used to adjust the pH of the binder composition to an acidic pH. Examples of suitable acidic pH adjusters include, but are not limited to, inorganic acids such as sulfuric acid, phosphoric acid, and boric acid, as well as 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. Inorganic salts may also act as acid precursors. The acids adjust the pH and, in some cases, act as crosslinking agents as discussed above. Organic and / or inorganic bases may be included to increase the pH of the binder composition. The bases may be volatile or nonvolatile. Examples of volatile bases include ammonia and alkyl-substituted amines, such as methylamine, ethylamine, or 1-aminopropane, dimethylamine, and ethylmethylamine. Examples of non-volatile bases include sodium hydroxide, potassium hydroxide, sodium carbonate, and t-butylammonium hydroxide.

[0037] When uncured, the pH of the binder composition may be in the range of about 2.0 to about 5.0, including all amounts and ranges in between. In any of the embodiments disclosed herein, the pH of the binder composition when uncured is about 2.2 to 4.0, including about 2.5 to 3.8 and about 2.6 to 3.5. After curing, the pH of the binder composition may rise to a pH of at least 5.0, including levels of about 6.5 to 8.8 or about 6.8 to 8.2.

[0038] The binder further comprises water for dissolving or dispersing active solids for application onto reinforcing fibers. The water may be added in an amount sufficient to dilute the aqueous binder composition to a viscosity suitable for application to reinforcing fibers and to achieve the desired solid content on the fibers. It has been found that the binder compositions of the present invention may contain lower solid content than conventional phenol-urea-formaldehyde or carbohydrate-based binder compositions. In particular, the binder compositions may contain, but are not limited to, 5-35% by mass of binder solids, 8-30% by mass, 10-25% by mass, 12-20% by mass, and 15-19% by mass of binder solids. This level of solid content indicates that the binder compositions of the subject may contain more water than conventional binder compositions. However, due to the high curing rate of the binder composition, the binder can be processed at high lamp moisture levels (approximately 8% to 10%), and the binder composition requires less moisture removal than conventional binder compositions. The binder content can be measured as loss on ignition (LOI). In any of the embodiments disclosed herein, the LOI is 1% to 20%, including, but not limited to, 5.5% to 17%, 8% to 15%, and 10% to 14.5%. The specific LOI of a product depends largely on the type of product produced.

[0039] In any of the embodiments disclosed herein, the aqueous binder composition may also contain one or more additives, such as coupling agents, fillers, crosslinking density improvers, deodorizers, antioxidants, dust suppressants, biocides, moisture-proofing agents, or combinations thereof. Optionally, the binder may also contain, but are not limited to, dyes, pigments, further 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 process and product performance. Such additives include lubricants, wetting agents, antistatic agents, and / or water-repellent agents. Additives may be present in the binder composition in trace amounts (e.g., <about 0.1% by mass of the binder composition) to about 10% by mass of the total solids of the binder composition.

[0040] In any of the embodiments disclosed herein, the aqueous binder composition may or may not contain monomeric carboxylic acid components. Exemplary monomeric polycarboxylic acid components include aconitic acid, adipic acid, azelaic acid, butanetetracarboxylic acid dihydrate, butanetricarboxylic acid, chloride anhydride, citraconic acid, citric acid, dicyclopentadiene-maleic acid adduct, diethylenetriaminepentaacetate pentasodium salt, dipentene-maleic anhydride adduct, endomethylenehexachlorophthalic anhydride, ethylenediaminetetraacetic acid (EDTA), fully maleated rosin, This product contains maleate-treated tall oil fatty acids, fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleate-treated rosin which is oxidized and desaturated to alcohol and then carboxylic acid with potassium peroxide, 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.

[0041] In any of the embodiments disclosed herein, the binder composition may not contain reducing sugars. Reducing sugars are a type of carbohydrate or sugar that contains a free aldehyde or ketone group and can donate electrons to another molecule. Since the binder composition does not contain reducing sugars, it cannot participate in the Maillard reaction, which is a process that occurs when reducing sugars react with amines. The Maillard reaction results in a brown binder composition, which is undesirable for the binder composition of the subject. The aqueous binder composition comprises a polycarboxylic acid-based crosslinking agent (e.g., polymer polycarboxylic acid) and a polyol having at least four hydroxyl groups (e.g., sugar alcohol). Exemplary aqueous binder compositions are shown in Table 1 below.

[0042] JPEG2026088138000002.jpg33167 Aqueous binder compositions according to various exemplary embodiments of this disclosure may further contain additional components such as catalysts / accelerators (e.g., sodium hypophosphite), surfactants and / or coupling agents (e.g., silane). Exemplary binder compositions containing such additional components are shown in Table 2 below.

[0043] JPEG2026088138000003.jpg60164

[0044] The aqueous binder composition is formulated so that the level of water-soluble material after curing is reduced, as determined by extracting the water-soluble material with deionized water at room temperature for 2 hours, using approximately 1000 g of deionized water per gram of binder. The higher the level of water-soluble material after curing, the more likely the cured material is to undergo leaching when 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 material after curing. In some exemplary embodiments, the binder composition has less than 5.5% by mass of water-soluble material after curing, including less than 5.0% by mass, 4.0% by mass, 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. It has been found that reducing the level of water-soluble material after curing to 6.0% by mass or less improves the tensile strength of the binder composition compared to other similar binder compositions having more than 6.0% by mass of water-soluble material after curing.

[0045] Furthermore, the aqueous binder compositions of the subject matter have a viscosity that provides a precise balance between binder viscosity, reduction of releases, and improvement of product performance. As shown in Table 3 below, aqueous binder compositions according to the concept of the present invention exhibit a viscosity of at least 10 cP at 40% solids at a temperature of 25°C, including at least 15 cP at 40% solids, at least 20 cP at 40% solids, and at least 30 cP at 40% solids. In any of the embodiments disclosed herein, the viscosity of the binder composition is 60 cP or less at 25°C and 40% or less solids, for example, 55 cP or less, 50 cP or less, 45 cP or less, or 40 cP or less. In contrast, as shown in Comparative Examples 2 and 4 in Table 3, binder compositions containing monomeric carboxylic acids and sorbitol exhibit a viscosity of less than 10 cP at 40% solids and 25°C. Furthermore, Comparative Examples 1 and 3 contain binder compositions comprising polyacrylic acid, sorbitol, and polyvinyl alcohol, exhibiting a solid content of 40% and viscosities of at least 60 cP and 67.5 cP or higher at 25°C. In contrast, the binder compositions of Examples 1 to 6 each exhibit a solid content of 40% and viscosities greater than 10 cP and less than 60 cP at 25°C, providing a particularly useful viscosity range. Furthermore, in any of the exemplary embodiments, the aqueous binder composition does not release isocyanate emissions during the manufacturing process of the fibrous insulation material, or releases isocyanate emissions that are essentially undetectable.

[0046] JPEG2026088138000004.jpg97167 The binder compositions disclosed herein can be used in the manufacture of fibrous insulation products, such as fiberglass or mineral wool insulation products. Accordingly, aspects of the concept of the present invention also relate to a method for producing an insulation product, comprising the step of bringing fibers into contact with the binder compositions disclosed herein. The insulation product may optionally include a facer on one or both of its main surfaces. The facer may be any type of facing substrate known in the art, such as a nonwoven mat, foil mat, polymer surfacering mat, or woven fabric.

[0047] The term “textile insulation products” is general and encompasses a variety of compositions, manufactured articles, and manufacturing processes. The textile insulation products of this disclosure include a plurality of randomly oriented fibers. In certain exemplary embodiments, the plurality of randomly oriented fibers are inorganic fibers, including, but are not limited to, glass fibers, glass wool fibers, mineral wool fibers, slag wool fibers, stone wool fibers, ceramic fibers, metal fibers, and combinations thereof.

[0048] Optionally, the fibers may include natural and / or synthetic fibers, such as carbon, polyester, polyethylene, polyethylene terephthalate, polypropylene, polyamide, aramid, and / or polyaramid fibers, and may be used in nonwoven fiber mats. The term “natural fiber” as used herein refers to plant fibers extracted from any part of a plant, including stems, seeds, leaves, roots, or phloem, but is not limited to these. Examples of natural fibers suitable for use as reinforcing fiber materials include woody fibers, cellulosic fibers, straw, wood chips, wood strands, cotton, jute, bamboo, ramie, bagasse, hemp, coir, linen, kenaf, sisal, flax, enekene, and combinations thereof. Fiber insulation products may be formed from a single type of fiber or from a combination of fiber types. For example, fiber insulation products may be formed from various combinations of glass fibers, or various combinations of different inorganic and / or natural fibers, depending on the desired application. In any of the embodiments disclosed herein, the insulation product is formed entirely from glass fibers.

[0049] Fiber insulation is typically manufactured by fusing a molten composition of polymer, glass, or other minerals and spinning the fibers from a fusing device such as a rotary spinner. To form the insulation product, the fibers generated by the rotary spinner are drawn downward from the spinner toward a conveyor by a blower. As the fibers move downward, a binder composition is sprayed onto the fibers, and the fibers are collected on a forming conveyor in a forming chamber, utilizing the vacuum drawn in from below through the fiber pack, to form a binder-filled fiber pack. The residual heat from the glass fibers and the airflow through the fiber pack during the forming operation are generally sufficient to volatilize most of the water from the binder before the glass fibers exit the forming chamber, thereby leaving the remaining components of the binder composition on the glass fibers as a viscous or semi-viscous high-solids liquid.

[0050] The binder-coated fiber pack, compressed by the airflow passing through it in the molding chamber, is then transferred from the molding chamber to a transfer zone, where it expands vertically due to the elasticity of the glass fibers. The expanded fiber pack is then heated, for example, by transporting it through a curing oven, in which heated air is blown through the fiber pack, evaporating any remaining water in the binder composition, curing the binder composition, and firmly bonding the glass fibers together. Furthermore, in a curing oven, the fiber pack can be compressed by upper and lower perforated oven conveyors to form the insulation layer of the fiber insulation product. The fiber pack may be compressed using upper and lower oven conveyors to give the insulation layer a predetermined thickness. The cured binder composition imparts strength and elasticity to the insulation layer. It is understood that drying and curing of the binder composition may be carried out in one or two different steps. A two-step process is generally known as B-stage curing. The curing oven may be operated at a temperature of 100°C to 325°C or 250°C to 300°C. The fiber pack 140 may remain in the curing oven for a sufficient time to crosslink (cure) the binder composition and form the insulation layer.

[0051] B-stage formation is a process in which a binder-coated fiber pack is heated to a tack-imparting temperature without crosslinking, thereby causing the binder composition to adhere to each other and bond the fibers in the system, forming a fiber precursor. Therefore, the B-staged fiber precursor is an intermediate but curable product. Often, B-staged products may be exposed to ambient temperatures for extended periods, which can easily lead to drying out and surface solidification of conventional formaldehyde-free B-staged fiber insulating precursors, resulting in poor bond formation between the binder composition and the fibers when forming the desired final product. As a result, the cured finished product exhibits low tensile strength due to insufficient bonding between the fibers and the binder composition. However, surprisingly, it has been found that the binder composition formed according to the concept of the present invention has improved shelf life and fiber wetting properties even after prolonged exposure to ambient conditions. Accordingly, in any of the embodiments disclosed herein, the B-staged fibrous insulation precursor has a drying time of at least 500 seconds, for example, at least 520 seconds, at least 540 seconds, at least 560 seconds, and at least 590 seconds, as measured by the CEM Smart 6 moisture balance. By increasing the drying time, the B-staged fibrous insulation precursor can be B-staged for a longer period without the formation of a film caused by the drying of the binder.

[0052] Furthermore, as described above, the binder composition according to the concept of the present invention exhibits a viscosity that is particularly beneficial for B-stage development of uncured products. Low-viscosity binder compositions tend to move / flow along the fibers due to the pull of gravity. As a result, the bottom of the product becomes binder-rich (high LOI) than the top of the product, where the binder is depleted (low LOI). This causes the B-staged product to be molded into the final cured thermal insulation product, and upon curing, results in a non-uniform product. To counteract the movement of binder due to gravity, the binder composition of the subject has increased viscosity, thereby reducing the movement of binder solids during B-stage development.

[0053] Fiber insulation products may be characterized and classified by many different properties, one of which is density. Density can range from approximately 0.2 pounds / cubic foot ("pcf") to approximately 10 pcf in height, depending on the product. Low-density or lightweight insulation battens and blankets typically have a density of approximately 0.2 pcf to approximately 5 pcf, more commonly approximately 0.3 pcf to approximately 4 pcf, and have a coating rate of approximately 2 to 13% LOI. Products such as residential insulation battens may fall into this group. Fiber insulation products can be supplied in other forms, including boards (heat-compressed vats) and molded media (alternative forms of heat-compressed vats), for use in different applications. Fiber insulation products also include higher density products having a density of about 10 pcf to about 20 pcf (and often having a binder LOI of more than 12%), and medium density products more typically having a density of about 1 pcf to about 10 pcf (and having a binder LOI of about 5 to 15%), such as boards and panels. Medium and higher density insulation products can be used in industrial and / or commercial applications, including, but are not limited to, metal building insulation, pipe or tank insulation, insulated ceiling and wall panels, duct boards and HVAC insulation, and insulation for home appliances and automobiles.

[0054] The molding or shaping may optionally include a further step during curing to compress, mold, or shape the product into a specific final shape. A rigid board is a type of shaping, and its shape is planar. Other shapings can be formed by a die or mold, or by other molding equipment. Rigidity can be imparted by the use of higher density fibers and / or the application of a higher level of binder. As an alternative to rotary filamentation, some fiber insulation products, particularly higher density nonwoven insulation products, can be manufactured by airlaid or wet-laid processes using ready-made fibers of glass, mineral wool, or polymers dispersed in random orientation and in contact with a binder to form the product. While the present invention has been described in general terms, further understanding can be gained by referring to the specific examples provided below, which are provided for illustrative purposes only and are not intended to be exhaustive or restrictive unless otherwise specified. [Examples]

[0055] (Example 1) Exemplary binder compositions were prepared as outlined in Table 4 below. Each binder composition contained polyacrylic acid crosslinking agent and monomer polyol in various mass ratios, but the molar equivalent ratio of carboxylic acid groups to hydroxyl groups was kept constant at 0.87:1. A comparative binder composition (Comparative Example A) containing both monomer polyol and polymer polyol (e.g., polyvinyl alcohol) was prepared. A second comparative example (Comparative Example B) containing polyacrylic acid and glycerol (three hydroxyl groups) was prepared. The binder premixes were diluted with water, and the various additives shown in Table 4 below were incorporated to prepare the final binder compositions.

[0056] JPEG2026088138000005.jpg100163

[0057] Fiberglass sheets were impregnated with each binder composition having a solids-based concentration of 8.0% by mass. The LOI of the cured fiberglass sheets was approximately 26%. The binder-impregnated fiberglass sheets were cured at 400°F for 3.5 minutes, and then immersed in water for 3 hours under ambient conditions. The aqueous extracts leached from the impregnated sheets were dried and quantified as a percentage of the cured binder in the binder-impregnated fiberglass sheets. This binder extract analysis correlates the crosslinking density of various polyols affecting high temperature / high humidity performance with the amount of leached extract that affects moisture sensitivity, high temperature / high humidity performance, binder corrosivity, and discoloration of the finished product when exposed to moisture.

[0058] As shown in Figure 1, the cured polyacrylic acid / sorbitol binder composition containing carboxylic acid groups in a molar equivalent ratio of 0.87:1 with hydroxyl groups exhibited a high crosslink density and the lowest amount of water-soluble substances. Therefore, fiber insulation products made using this composition show reduced susceptibility to moisture due to this increased crosslink density. In addition, when the product is exposed to moisture (water runoff), the amount of solid material blooming on the surface is also reduced.

[0059] (Example 2) Fiberglass sheets impregnated with the binder compositions outlined in Table 4 above, having a dry solids content of 30%, Comparative Example B, Example A, Example C, Example D, and Example E. The binder-impregnated fiberglass sheets were dried using a commercially available CEM Smart 6 moisture analyzer, which rapidly analyzes moisture and solids in any product using a combination of infrared and microwave. Specific test conditions are shown below:

[0060] JPEG2026088138000006.jpg221164

[0061] Test procedure: 1. Weigh two sample pads. 2. Place one sample pad on the sample press. 3. Using a dispensing pipette, evenly apply 2 ml of binder solution (30% dry solids concentration) to the sample pad. 4. Cover the sample pad with the second sample pad - the binder is "sandwiched" between the sample pads.

[0062] 5. Press the sample pad with a CEM press to achieve a uniform binder distribution. 6. Place the sample pad in the CEM sample holder. 7. Start the measurement. 8. Record the execution time of the drying experiment upon completion of the measurement (read from the test data provided by the test equipment).

[0063] Figure 2 shows the drying times of each binder-impregnated fiberglass sheet in the CEM Smart 6. As shown, the sheets formed using either Example E or Example A showed the longest drying times, at 549.5 seconds and 597 seconds, respectively, indicating a longer shelf life for the B-staged uncured fiberglass product. It also shows that longer drying times broaden the processing window of the fiberglass insulation product being produced (slower drying on the "lamp" and moisture is retained throughout the uncured product before entering the curing oven), resulting in a more uniformly cured product and improved product consistency. The slower drying time ensures that the uncured fiberglass on the lamp remains moist, guaranteeing that the uncured fiberglass product has an inherently uniform moisture distribution during curing. This results in more uniform properties (e.g., bond strength) in the finished product.

[0064] (Example 3) Using Example E and Comparative Examples A and B from Table 4 above, B-staged fiberglass rolls with a 9% LOI were formed. Additional comparative examples were prepared using a phenolurea-formaldehyde binder composition. The rolls were stored under different humidity conditions and weighed at periodic intervals. The staining behavior of each binder-impregnated fiberglass roll was observed under each condition. Figure 3 shows the mass loss of each fiberglass roll measured at cyclic time intervals at 25°C and 46% humidity. The fiberglass rolls were weighed initially, and then at 2.5 minutes, 5 minutes, 7.5 minutes, 10 minutes, 30 minutes, 60 minutes, and 240 minutes. As shown, the samples formed using Example E showed a low level of mass loss, similar to the samples formed using the conventional phenolurea-formaldehyde binder composition. Figure 4 similarly shows the mass loss of each fiberglass roll measured at periodic intervals, but only at 75% humidity. The fiberglass rolls were weighed first, and then at 2.5 minutes, 5 minutes, 7.5 minutes, 10 minutes, 30 minutes, 60 minutes, and 240 minutes. The results show that, at high humidity levels, the sample produced using Example E exhibited the lowest mass loss among the formaldehyde-free binder compositions tested, and had a similar mass loss profile to the sample formed using the conventional phenolurea-formaldehyde binder composition. In contrast, the sample formed using the binder composition of Comparative Example A showed the highest mass loss, indicating that the binder composition dried faster than the others.

[0065] Figure 5 shows the mass loss of each fiberglass roll measured after 10 minutes at 46%, 74%, and 75% humidity and 25°C. The results show that at high humidity levels (74% and 75%), the samples prepared using the binder composition of Example E exhibited the lowest drying rates among the tested formaldehyde-free binder compositions (0.012 g / min and 0.013 g / min, respectively), confirming that they had a similar drying rate to the samples formed using the conventional phenolurea-formaldehyde binder composition. In contrast, the samples formed using the binder compositions of Comparative Example A, which included a polymer polyol in addition to the monomer polyol, or Comparative Example B, which included polyacrylic acid and glycerol, exhibited the highest drying rates, indicating that the binder compositions dried faster than the others. Many of the more detailed embodiments of the illustrated products and processes are largely known in the art, and it will be understood that these embodiments have been omitted for the purpose of briefly presenting the general concept of the invention. Although the invention has been described with reference to specific means, materials and embodiments, those skilled in the art will readily be able to identify the essential features of this disclosure from the foregoing description and will be able to make various changes and modifications to adapt to various uses and features without departing from the spirit and scope of the invention as described above and in the appended claims.

[0066] Item 1. An aqueous binder composition comprising a crosslinking agent containing a monomer polyol having at least four hydroxyl groups in an amount of 5.0 to 50.0% by mass relative to the total solids content of the aqueous binder composition, and a polymer polycarboxylic acid having at least two carboxylic acid groups in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition, wherein the molar equivalent ratio of carboxylic acid groups to hydroxyl groups is 0.15 / 1 to 2.23 / 1 or 0.60 / 1.0 to 1.0 / 0.6, and the aqueous binder composition has a pH of 2.2 to 4.0, a solids content of 40%, and a viscosity of 10 cP to 60 cP at 25°C. Item 2. The aqueous binder composition according to Item 1, wherein the crosslinking agent is polyacrylic acid. Item 3. The aqueous binder composition according to any one of items 1 to 2, wherein the crosslinking agent is present in the binder composition in an amount of 52.0 to 72% by mass relative to the total solid content of the aqueous binder composition. Item 4. An aqueous binder composition according to any one of items 1 to 3, wherein the monomer polyol comprises at least five hydroxyl groups.

[0067] Item 5. An aqueous binder composition according to any one of items 1 to 4, wherein the ratio of molar equivalents of carboxylic acid groups to hydroxyl groups is 0.26 / 1 to 0.75 / 1 or 0.80 / 1.0 to 1.0 / 0.8. Item 6. An aqueous binder composition according to any one of items 1 to 5, wherein the monomer polyol comprises one or more of sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, short-chain alkanolamines, and mixtures thereof. Item 7. An aqueous binder composition according to any one of items 1 to 6, wherein the monomer polyol is selected from the group consisting of pentaerythritol, xylitol, sorbitol and mixtures thereof. Item 8. The aqueous binder composition according to any one of items 1 to 7, wherein the monomer polyol is present in the binder composition in an amount of 15 to 37% by mass relative to the total solids content of the aqueous binder composition. Item 9. An aqueous binder composition according to any one of items 1 to 8, which does not contain polymer polyhydroxy compounds.

[0068] Item 10. An aqueous binder composition according to any one of items 1 to 9, which does not contain a monomeric carboxylic acid. Item 11. An aqueous binder composition according to any one of items 1 to 10, having a solid content of 40% and a viscosity of 25 cP to less than 60 cP at 25°C. Item 12. Multiple randomly oriented fibers, and A fiber insulation product comprising a crosslinked formaldehyde-free binder composition that at least partially coats the fibers, The cross-linked formaldehyde-free binder composition contains less than 5.5% by mass of water-soluble material. At least one monomer polyol having at least four hydroxyl groups, in an amount of 5.0 to 50.0% by mass relative to the total solid content of the aqueous binder composition; and A crosslinking agent containing a polymer polycarboxylic acid having at least two carboxylic acid groups, in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. A fibrous heat insulating product formed from an aqueous binder composition comprising, wherein the binder composition has an uncured pH of 2.2 to 4.0 and a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.15 / 1 to 2.23 / 1 or 0.60 / 1.0 to 1.0 / 0.6. Item 13. The thermal insulation product described in Item 12, wherein the fibers include one or more of mineral fibers, natural fibers, and synthetic fibers. Item 14. A fiber insulation product as described in Item 12 or 13, wherein the fibers include glass fibers, mineral wool fibers, or mixtures thereof.

[0069] Item 15. A fibrous insulation product according to any one of items 12 to 14, wherein the aqueous binder composition does not contain a polymer polyhydroxy compound. Item 16. A fibrous insulation product according to any one of items 12 to 15, wherein the ratio of molar equivalents of carboxylic acid groups to hydroxyl groups is 0.26 / 1 to 0.75 / 1 or 0.80 / 1.0 to 1.0 / 0.8. Item 17. A fibrous insulation product according to any one of items 12 to 16, wherein the monomer polyol comprises one or more of sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, short-chain alkanolamines, and mixtures thereof. Item 18. Fiber insulation products as described in any of items 12 to 17, including one or more of ceiling boards, duct boards, foundation boards, pipe and tank insulation, sound-absorbing panels, acoustic panels, duct liners, residential insulation, duct traps, metal building insulation, and flexible duct media. Item 19. A fibrous insulation product as described in any of Items 12 to 18, wherein the insulation product contains 5.5% to 17% binder LOI.

[0070] Item 20. Multiple randomly oriented fibers; and An uncured aqueous binder composition that at least partially coats the aforementioned fibers. A B-stage fibrous insulation product comprising the aqueous binder composition, At least one monomer polyol having at least four hydroxyl groups, in an amount of 5.0 to 50.0% by mass relative to the total solid content of the aqueous binder composition; and A crosslinking agent containing a polymer polycarboxylic acid having at least two carboxylic acid groups, in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. The uncured aqueous binder composition contains 40% solids and has a viscosity of 10 cP to 60 cP at 25°C. B-stage crystalline insulation products have a drying time of at least 500 seconds, as measured by the CEM Smart 6 moisture analyzer. Fiber insulation product that can be converted to B-stage. Item 21. A B-stageable fiber insulation product according to Item 20, wherein the uncured aqueous binder composition has a solid content of 40% and a viscosity of 30 cP to 45 cP at 25°C.

[0071] Item 22. A B-stageable fiber insulation product according to item 20 or 21, wherein the crosslinking agent is polyacrylic acid. Item 23. A B-stageable fiber insulation product according to any one of items 20 to 22, wherein the aqueous binder composition has a pH of 2.2 to 4.0. Item 24. A B-stageable fiber insulation product according to any one of items 20 to 23, wherein the aqueous binder composition has a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.15 / 1 to 2.23 / 1 or 0.60 / 1.0 to 1.0 / 0.6. Item 25. A B-stageable fiber insulation product according to any of items 20 to 24, wherein the monomer polyol comprises one or more of sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, short-chain alkanolamines, and mixtures thereof. Item 26. A B-stageable fiber insulation product according to any of items 20 to 25, wherein the composition does not contain polymer polyhydroxy compounds. Item 27. A B-stageable fiber insulation product according to any of items 20 to 26, wherein the composition does not contain a monomeric carboxylic acid.

[0072] Item 28. A method for producing a fibrous thermal insulation product having a low level of water-soluble material, The step involves applying a formaldehyde-free binder composition to multiple fibers, wherein the formaldehyde-free binder composition is At least one monomer polyol having at least four hydroxyl groups, in an amount of 5.0 to 50.0% by mass relative to the total solid content of the aqueous binder composition; and A crosslinking agent containing a polymer polycarboxylic acid having at least two carboxylic acid groups, in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. Steps including, The steps of gathering fibers onto a substrate to form a binder-filled fiber pack; and Steps to cure the binder-filled fiber pack A method comprising a fiber insulation product containing less than 5.5% by mass of water-soluble material. Item 29. A method for producing a fibrous thermal insulation product according to Item 28, wherein the formaldehyde-free binder composition comprises a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.15 / 1 to 2.23 / 1 or 0.60 / 1.0 to 1.0 / 0.6.

[0073] Item 30. A method for producing a fibrous insulation product according to any one of items 28 to 29, wherein the formaldehyde-free binder composition has a pH of 2.2 to 4.0. Item 31. A method for producing a fibrous insulation product according to any one of items 28 to 30, wherein the formaldehyde-free binder composition has a solid content of 40% and a viscosity of 10 cP to 60 cP at 25°C. Item 32. A method for B-stage preparation of a fibrous insulation material precursor, The step involves applying a formaldehyde-free binder composition to multiple fibers to form a binder-impregnated fiber insulating material precursor, wherein the binder composition is At least one monomer polyol having at least four hydroxyl groups, in an amount of 5.0 to 50.0% by mass relative to the total solid content of the aqueous binder composition; and A crosslinking agent containing a polymer polycarboxylic acid having at least two carboxylic acid groups, in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. Steps including The binder-impregnated fiber insulation precursor is exposed to ambient temperature for at least 500 seconds to form a B-stage fiber precursor without the binder composition forming a film on the surface of the fiber insulation precursor. A method that includes this.

[0074] Item 33.5.0 to 50.0% by mass of at least one monomer polyol having at least four hydroxyl groups; 55.0-62% by mass of polyacrylic acid crosslinking agent; 0.5 to 5.0 mass% of catalyst; 2.0 to 15.0% by mass of processing aids; 0-5.0% by mass of surfactant; 0-2.0% by mass of pigment; and 0-15% by mass of silicone An aqueous formaldehyde-free binder composition comprising, wherein the percentage is based on the total solids content of the aqueous binder composition, the molar equivalent ratio of carboxylic acid groups to hydroxyl groups is 0.26 / 1 to 0.75 / 1 or 0.8 / 1 to 1 / 0.8, and the aqueous binder composition has a pH of 2.2 to 4.0, a solids content of 40%, and a viscosity of 30 cP to 55 cP at 25°C.

Claims

1. A monomer polyol having at least four hydroxyl groups, in an amount of 5.0 to 50.0% by mass relative to the total solids content of the aqueous binder composition; and A crosslinking agent containing a polymer polycarboxylic acid having at least two carboxylic acid groups, in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. An aqueous binder composition comprising the above, wherein the molar equivalent ratio of carboxylic acid groups to hydroxyl groups is 0.15 / 1.0 to 2.23 / 1, and the aqueous binder composition has a pH of 2.2 to 4.0, a solid content of 40%, and a viscosity of 10 cP to 60 cP at 25°C.

2. The aqueous binder composition according to claim 1, wherein the crosslinking agent is polyacrylic acid.

3. The aqueous binder composition according to claim 1, wherein the crosslinking agent is present in the binder composition in an amount of 52.0 to 72% by mass relative to the total solid content of the aqueous binder composition.

4. The aqueous binder composition according to claim 1, wherein the monomer polyol comprises at least five hydroxyl groups.

5. The aqueous binder composition according to claim 1, wherein the ratio of molar equivalents of carboxylic acid groups to hydroxyl groups is 0.26 / 1 to 0.75 / 1.

6. The aqueous binder composition according to claim 1, wherein the monomer polyol comprises one or more of sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, short-chain alkanolamines, and mixtures thereof.

7. The aqueous binder composition according to claim 1, wherein the monomer polyol is selected from the group consisting of pentaerythritol, xylitol, sorbitol, and mixtures thereof.

8. The aqueous binder composition according to claim 1, wherein a monomer polyol is present in the binder composition in an amount of 15 to 37% by mass relative to the total solid content of the aqueous binder composition.

9. The aqueous binder composition according to claim 1, which does not contain polymer polyhydroxy compounds.

10. The aqueous binder composition according to claim 1, which does not contain monomeric carboxylic acids.

11. The aqueous binder composition according to claim 1, having a solid content of 40% and a viscosity of 25 cP to less than 60 cP at 25°C.

12. Multiple randomly oriented fibers, and A cross-linked formaldehyde-free binder composition that at least partially coats the fibers. A fiber insulation product that includes, A fibrous heat insulating product formed from the aqueous binder composition according to claim 1, wherein the crosslinked formaldehyde-free binder composition contains less than 5.5% by mass of a water-soluble material.

13. The thermal insulation product according to claim 12, wherein the fibers include one or more of mineral fibers, natural fibers, and synthetic fibers.

14. The fiber insulation product according to claim 12, wherein the fibers include glass fibers, mineral wool fibers, or mixtures thereof.

15. The fiber insulation product according to claim 12, wherein the aqueous binder composition does not contain a polymer polyhydroxy compound.

16. The fiber insulation product according to claim 12, wherein the ratio of molar equivalents of carboxylic acid groups to hydroxyl groups is 0.26 / 1.0 to 0.75 / 1.

17. The fiber insulation product according to claim 12, wherein the monomer polyol comprises one or more of sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, short-chain alkanolamines, and mixtures thereof.

18. The fiber insulation product according to claim 12, comprising one or more of the following: ceiling boards, duct boards, foundation boards, pipe and tank insulation materials, sound-absorbing boards, acoustic panels, duct liners, residential insulation materials, duct traps, metal building insulation materials, and flexible duct media.

19. The fiber insulation product according to claim 12, comprising 5.5% to 17% binder LOI.

20. Multiple randomly oriented fibers; and An uncured aqueous binder composition that at least partially coats the aforementioned fibers. A fiber insulation product that can be B-staged, comprising the aqueous binder composition, At least one monomer polyol having at least four hydroxyl groups, in an amount of 5.0 to 50.0% by mass relative to the total solid content of the aqueous binder composition; and A crosslinking agent containing a polymer polycarboxylic acid having at least two carboxylic acid groups, in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. The uncured aqueous binder composition contains 40% solids and has a viscosity of 10 cP to 60 cP at 25°C. B-stage crystalline insulation products have a drying time of at least 500 seconds, as measured by a CEM Smart 6 moisture analyzer. Fiber insulation product that can be converted to B-stage.

21. The B-stageable fiber insulation product according to claim 20, wherein the uncured aqueous binder composition has a solid content of 40% and a viscosity of 30 cP to 45 cP at 25°C.

22. The B-stage compliant fiber insulation product according to claim 20, wherein the crosslinking agent is polyacrylic acid.

23. The B-stageable fiber insulation product according to claim 20, wherein the aqueous binder composition has a pH of 2.2 to 4.

0.

24. The B-stageable fiber insulation product according to claim 20, wherein the aqueous binder composition has a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.60 / 1.0 to 1.0 / 0.

6.

25. The B-stageable fiber insulation product according to claim 20, wherein the monomer polyol comprises one or more of sugar alcohols, pentaerythritol, primary alcohols, 1,2,4-butanetriol, trimethylolpropane, short-chain alkanolamines, and mixtures thereof.

26. The B-stageable fiber insulation product according to claim 20, wherein the composition does not contain a polymer polyhydroxy compound.

27. The B-stageable fiber insulation product according to claim 20, wherein the composition does not contain a monomeric carboxylic acid.

28. A method for producing a fibrous thermal insulation product having a low level of water-soluble material, The step involves applying a formaldehyde-free binder composition to multiple fibers, wherein the formaldehyde-free binder composition is At least one monomer polyol having at least four hydroxyl groups, in an amount of 5.0 to 50.0% by mass relative to the total solid content of the aqueous binder composition; and A crosslinking agent containing a polymer polycarboxylic acid having at least two carboxylic acid groups, in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. Steps including, The steps of gathering fibers onto a substrate to form a binder-filled fiber pack; and Steps to cure the binder-filled fiber pack A method comprising a fiber insulation product containing less than 5.5% by mass of water-soluble material.

29. A method for producing a fibrous heat insulating product according to claim 28, wherein the formaldehyde-free binder composition comprises a molar equivalent ratio of carboxylic acid groups to hydroxyl groups of 0.15 / 1.0 to 2.23 / 1.

30. A method for producing a fibrous heat insulating product according to claim 28, wherein the formaldehyde-free binder composition has a pH of 2.2 to 4.

0.

31. A method for producing a fibrous heat insulating product according to claim 28, wherein the formaldehyde-free binder composition has a solid content of 40% and a viscosity of 10 cP to 60 cP at 25°C.

32. A method for B-stage preparation of a fibrous insulation material precursor, The step involves applying a formaldehyde-free binder composition to multiple fibers to form a binder-impregnated fiber insulating material precursor, wherein the binder composition is At least one monomer polyol having at least four hydroxyl groups, in an amount of 5.0 to 50.0% by mass relative to the total solid content of the aqueous binder composition; and A crosslinking agent containing a polymer polycarboxylic acid having at least two carboxylic acid groups, in an amount of at least 50.0% by mass relative to the total solids content of the aqueous binder composition. Steps including, The binder-impregnated fiber insulation precursor is exposed to ambient conditions for at least 5 minutes to form a B-stage fiber precursor without the binder composition forming a film on the surface of the fiber insulation precursor. A method that includes this.

33. 5.0 to 37.0% by mass of at least one monomer polyol having at least four hydroxyl groups; 50.0 to 62% by mass of polyacrylic acid crosslinking agent; 0.5 to 5.0 mass% of catalyst; 2.0 to 15.0% by mass of processing aids; 0-5.0% by mass of surfactant; 0 to 2.0% by mass of pigment; and 0-15% by mass of silicone An aqueous formaldehyde-free binder composition comprising the following, wherein each percentage is based on the total solids content of the aqueous binder composition, the molar equivalent ratio of carboxylic acid groups to hydroxyl groups is 0.26 / 1 to 0.75 / 1, and the aqueous binder composition has a pH of 2.2 to 4.0, a solids content of 40%, and a viscosity of 30 cP to 55 cP at 25°C.

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