Aqueous binder composition for mineral wool products

Abstract

A method for making an insulation product is provided, comprising collecting a plurality of inorganic fibers comprising at least 25 weight percent divalent and trivalent metal oxides on a substrate, applying a formaldehyde-free aqueous binder composition comprising a nitrogen-based protective agent to the collection of inorganic fibers, removing the nitrogen-based protective agent by heating the binder-coated inorganic fibers; and curing the aqueous binder composition by an esterification reaction.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and any benefit of U.S. Provisional Application No. 63 / 073,013, filed on September 1, 2020, the contents of which are incorporated by reference in their entirety into this application. Background Art

[0003] Aqueous binder compositions are commonly used to form woven and nonwoven fiber products, such as insulation products, composite products, wood fiberboard, etc. Insulation products, such as those formed from inorganic fibers, are typically manufactured by fiberizing a molten glass or mineral-based composition and spinning fibers from a fiberizing device (e.g., a rotary spinner). To form the insulation product, the fibers produced by the rotary spinner are pulled 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 in a high-loft continuous blanket on the conveyor. The binder material imparts resilience to the insulation product after packaging and provides rigidity and workability, allowing the insulation product to be handled and applied in the insulation cavity of a building as needed. The binder composition also protects the fibers from interfilament wear and promotes compatibility between individual fibers. The blanket containing the binder-coated fibers is then passed through a curing oven, and the binder is cured to set the blanket to the desired thickness.

[0004] After the binder cures, the fibrous insulation can be cut into lengths to form individual insulation products, and the insulation products can be packaged for shipment to customer locations. Insulation products prepared in this manner can be provided in a variety of forms, including batts, blankets, and boards (heated and compressed batts) for different applications.

[0005] Mineral fiber products typically include man-made vitreous fibers (MMVF), such as glass fibers, ceramic fibers, basalt fibers, slag wool, mineral wool, and rockwool, bonded together by a polymeric binder composition. Conventional binder compositions for mineral fiber insulation, particularly mineral wool insulation, are based on phenol-formaldehyde (PF) resins, and PF resins extended with urea (PUF resins). However, while such binder compositions provide suitable properties for insulation products, formaldehyde binders release undesirable emissions during manufacturing, and there is a desire to move away from formaldehyde-based binders.

[0006] As an alternative to formaldehyde-based binders, certain formaldehyde-free formulations have been developed for use as binders in insulation products. Such formaldehyde-free formulations may include polycarboxylic acids and polyhydroxy components intended to crosslink via an esterification reaction. Such polycarboxylic acid-based binder compositions are typically acidic, with a pH of less than 5. However, mineral wool fibers are highly alkaline, with higher concentrations of divalent and trivalent metal oxides in the fibers than other inorganic fibers (such as glass fibers). Consequently, the polycarboxylic acid groups in conventional binder compositions react irreversibly with the metal oxides of the mineral wool fibers upon application, which prevents the acid groups from being available for esterification with the polyhydroxy crosslinker. Consequently, acidic binders tend to lack the strength of PF binders when used with mineral wool, and products formed therefrom exhibit insufficient performance.

[0007] Therefore, there is a need for a formaldehyde-free binder composition for use in the production of insulation products using high basicity fibers such as mineral wool. Summary of the Invention

[0008] Various exemplary aspects of the present inventive concepts relate to a method for making an insulation product, the method comprising collecting a plurality of inorganic fibers on a substrate, the inorganic fibers being prepared from a composition comprising at least 25 wt% of divalent and trivalent metal oxides; applying an aqueous binder composition to the collection of inorganic fibers; and forming a binder-coated inorganic fiber. The aqueous binder composition comprises at least 50 wt% solids of a crosslinker comprising at least two carboxylic acid groups; 10.0 to 40.0 wt% solids of a polyol component having at least two hydroxyl groups; and 1.25-50.0 wt% solids of a nitrogen-based protective agent. The nitrogen-based protective agent temporarily blocks at least 40% of the carboxylic acid groups of the crosslinker. The method further comprises removing the nitrogen-based protective agent by heating the binder-coated inorganic fibers to a temperature of at least 150°C; and curing the aqueous binder composition by an esterification reaction between the crosslinker and the polyol component to form an inorganic fiber insulation product, wherein the aqueous binder composition does not contain added formaldehyde.

[0009] In any of the exemplary embodiments, the crosslinking agent is present in the binder composition in an amount of 55 wt % to 85 wt % solids, based on the total solids content of the aqueous binder composition.

[0010] In any exemplary embodiment, the polyol component includes a sugar alcohol, an alkanolamine, pentaerythritol, or a mixture thereof.

[0011] Nitrogen-based protecting agents may include ethylenediamine, ammonium hydroxide, ethylenediaminetetraacetic acid, or mixtures thereof.

[0012] In any exemplary embodiment, the aqueous binder composition has an uncured pH of 4.0-7.0, such as 4.2 to 6.5, and 4.3 and 6.3.

[0013] In any exemplary embodiment, the insulation product has a longitudinal tensile strength according to EN 1607 of at least 30 kPa immediately upon manufacture.

[0014] In any exemplary embodiment, the insulation product retains at least 50% of its tensile strength after 7 days in a tropical oven at a temperature of 65°C and 95% relative humidity, and in any exemplary embodiment, the insulation product retains at least 60% of its tensile strength after 7 days in a tropical oven at a temperature of 65°C and 95% relative humidity.

[0015] In any exemplary embodiment, the insulation product has a compressive strength at 10% strain according to EN 826 of at least 10 kPa.

[0016] Other exemplary aspects of the present inventive concepts relate to fiber products comprising a plurality of randomly oriented mineral wool fibers and an ester-crosslinked thermosetting binder composition that at least partially coats the fibers. Prior to crosslinking, the binder composition comprises an aqueous composition comprising: at least 50 wt% solids of a crosslinker comprising at least two carboxylic acid groups; 10.0 to 40.0 wt% solids of at least one polyol having at least two hydroxyl groups, based on the total solids content of the aqueous binder composition; and 1.25 to 50.0 wt% solids of a nitrogen-based protective agent. Prior to crosslinking, the nitrogen-based protective agent temporarily blocks at least 40% of the carboxylic acid groups of the crosslinker. The mineral wool insulation product has a longitudinal tensile strength of at least 30 kPa according to EN 1607 immediately upon manufacture and retains at least 50% of the tensile strength after 7 days under hot / humid conditions. In any exemplary embodiment, it retains at least 60% of the tensile strength after 7 days in a hot box at a temperature of 65°C and 95% relative humidity.

[0017] In any of the exemplary embodiments, the fibrous product includes any of an insulation product, a nonwoven mat, particle board, ceiling board, and duct board.

[0018] The crosslinking agent may be present in the binder composition in an amount of 60-82 wt % based on the total solids content of the aqueous composition.

[0019] The polyol component includes a sugar alcohol, an alkanolamine, pentaerythritol, or a mixture thereof. In any exemplary embodiment, the polyol component includes sorbitol, triethanolamine, pentaerythritol, or a mixture thereof.

[0020] In any exemplary embodiment, the fibrous product has a compressive strength at 10% strain according to EN 826 of at least 10 kPa.

[0021] Other exemplary aspects of the present inventive concepts relate to an aqueous binder composition comprising at least 50 wt% solids of a polymeric crosslinker comprising at least two carboxylic acid groups; at least 8.0 wt% solids of a protective agent comprising one or more amine groups; and 10.0 to 35.0 wt% solids of at least one polyol component having at least two hydroxyl groups. The binder composition has a crosslinker to nitrogen-based protective agent ratio of 4:1 to 1.5:1 and an uncured pH of at least 4.5. Prior to curing the binder composition, at least 40% of the carboxylic acid groups are temporarily blocked by the nitrogen-based protective agent.

[0022] The crosslinking agent may be present in the aqueous binder composition in an amount of 60 to 82 wt % based on the total solids content of the aqueous binder composition.

[0023] The polyol component may include one or more of a sugar alcohol, an alkanolamine, pentaerythritol, or a mixture thereof. In any exemplary embodiment, the polyol component includes sorbitol, triethanolamine, pentaerythritol, or a mixture thereof.

[0024] Many other aspects, advantages and / or features of the general inventive concept will become more apparent from the following detailed description of exemplary embodiments and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The general inventive concept as well as its illustrated embodiments and advantages are described in more detail below by way of example with reference to the accompanying drawings, in which:

[0026] Figure 1 Illustrated is an exemplary esterification reaction with limited crosslinking due to the formation of a carboxylate metal complex between mineral wool fibers and an unprotected carboxylic acid.

[0027] Figure 2 An exemplary esterification reaction using a partially protected carboxylic acid-based binder is illustrated.

[0028] Figure 3 An exemplary method for producing a mineral wool product according to the present invention is illustrated. DETAILED DESCRIPTION

[0029] Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as those generally understood by those skilled in the art to which these exemplary embodiments belong. The terms used in the description of this application are only used to describe exemplary embodiments and are not intended to limit exemplary embodiments. Therefore, the overall inventive concept is not intended to be limited to the specific embodiments shown in this application. Although other methods and materials similar or equivalent to those described in this application can be used in the practice or testing of the present invention, the application describes preferred methods and materials.

[0030] As used in the 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.

[0031] "Substantially free" means that the composition includes less than 1.0 wt% of the component, including no more than 0.8 wt%, no more than 0.6 wt%, no more than 0.4 wt%, no more than 0.2 wt%, no more than 0.1 wt% and no more than 0.05 wt%. In any exemplary embodiment, "substantially free" means that the composition includes no more than 0.01 wt% of the component.

[0032] Unless otherwise indicated, all numbers used in the specification and claims expressing amounts of ingredients, chemical and molecular properties, reaction conditions, and the like should be understood as being modified in all instances by the term "about." Therefore, unless otherwise indicated, the numerical parameters set forth in the specification and the appended claims are approximate and may vary depending upon the desired properties sought to be obtained by the exemplary embodiments. At the very least, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding techniques.

[0033] Unless otherwise stated, 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 clearly disclosed in the embodiment. It will be readily understood that the features of the description associated with any particular aspect described herein may be applicable to other aspects described herein, as long as the features are compatible with the aspects. In particular: the features described herein with respect to the method may be applicable to fiber products, and vice versa, the features described herein with respect to the method may be applicable to aqueous binder compositions, and vice versa, and the features described herein with respect to fiber products may be applicable to aqueous binder compositions, and vice versa.

[0034] Every numerical range given throughout the specification and claims will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0035] The present specification relates to formaldehyde-free or "no added formaldehyde" 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 used interchangeably and are synonymous.

[0036] The binder composition can be used to make fiber insulation products and related products, such as fiber-reinforced felts, yarns, nonwovens, and the like (hereinafter collectively referred to as fiber products). The binder composition can be used in particular with rock or mineral wool products (such as mineral wool insulation products) made with the cured binder composition. Other products may include composite products, wood fiberboard products, metal building insulation, pipe insulation, ceiling tiles, ceiling tiles, "heavy density" products such as ceiling tiles, pipe wraps, pipe liners, and "light density" products. Additional fiber products include nonwoven fiber mats and particleboard, and composite products made therefrom.

[0037] The present inventive concept is based on the discovery that by temporarily blocking a percentage of the carboxylic acid functional groups, an acidic binder composition can be applied to mineral wool fibers without damaging the fibers or affecting the ability of the binder composition to effectively crosslink by esterification to form an effective ester-crosslinked thermosetting binder composition without the addition of formaldehyde.

[0038] Fibers suitable for use in the fiber products of the present disclosure include, but are not limited to, mineral fibers (e.g., mineral wool, rock wool, asbestos, slag wool, etc.), glass fibers, carbon fibers, ceramic fibers, natural fibers, and synthetic fibers. In certain exemplary embodiments, the plurality of randomly oriented fibers are mineral wool fibers, including, but not limited to, mineral wool fibers, rock wool fibers, slag wool fibers, asbestos fibers, or combinations thereof.

[0039] Fibrous insulation products can be formed entirely from one type of fiber, or they can be formed from a combination of two or more types of fibers. For example, depending on the desired application, the insulation product can be formed from a combination of various types of mineral fibers or various combinations of different inorganic fibers and / or natural fibers. In certain exemplary embodiments, the insulation product is formed entirely from mineral wool fibers.

[0040] Compared to glass fibers used for insulation, mineral wool typically has a higher percentage of divalent and trivalent metal oxides. Table 1 provides a typical range of glass wool formulations and a typical range of stone (or mineral) wool formulations. Guldberg, Marianne et al., "The Development of Glass and Stone Wool Compositions with Increased Biosolubility" Regulatory Toxicology and Pharmacology 32, 184-189 (2000). As shown below, glass wool has a total weight percentage of divalent and trivalent oxides (CaO / MgO / Al2O3 / FeO) of no more than 25 wt%. In contrast, mineral wool or stone wool contains a minimum of 25 wt% divalent and trivalent metal oxides, or in some cases, more than 30 wt% divalent and trivalent metal oxides, and in some cases at least 50 wt% divalent and trivalent metal oxides. Such metal oxides, especially aluminum, have a strong tendency to complex with acidic functional groups such as carboxylic acids, which inhibits wetting of the binder on the fiber and prevents adequate esterification and crosslinking. Therefore, conventional acidic formaldehyde-free binders exhibit reduced performance with mineral wool fibers.

[0041] Table 1

[0042] Traditional insulation cotton composition (weight %)

[0043]

[0044] The present binder composition includes an acidic crosslinking agent suitable for crosslinking with the polyol component via an esterification reaction. In any exemplary embodiment, the crosslinking agent may have a number average molecular weight greater than 90 Daltons, such as from about 90 Daltons to about 10,000 Daltons, or from about 190 Daltons to about 5,000 Daltons. In any exemplary embodiment, the crosslinking agent has a number average molecular weight of from about 2,000 Daltons to 5,000 Daltons, or about 4,000 Daltons.

[0045] Non-limiting examples of suitable crosslinking agents include materials having one or more carboxylic acid groups (-COOH), such as monomeric and polymeric polycarboxylic acids, including salts or anhydrides thereof, and mixtures thereof. In any exemplary embodiment, the polycarboxylic acid can be a polymeric polycarboxylic acid, such as a homopolymer or copolymer of acrylic acid. The polymeric polycarboxylic acid can include polyacrylic acid (including salts or anhydrides thereof) and polyacrylic acid-based resins, such as QR-1629S and Acumer 9932, both commercially available from Dow Chemical Company, a polyacrylic acid composition commercially available from CH Polymer, and a polyacrylic acid composition commercially available from Coatex. Acumer 9932 is a polyacrylic acid / sodium hypophosphite resin having a molecular weight of approximately 4000 and a sodium hypophosphite content of 6-7 wt %, based on the total weight of the polyacrylic acid / sodium hypophosphite resin. QR-1629S is a polyacrylic acid / glycerol resin composition.

[0046] In any exemplary embodiment disclosed herein, the crosslinking agent may be present in the binder composition in an amount of at least 50 wt %, based on the total solids content of the binder composition, including but not limited to at least 55 wt %, at least 60 wt %, at least 63 wt %, at least 65 wt %, at least 68 wt %, at least 70 wt %, at least 71 wt %, at least 73 wt %, and at least 75.0 wt %. In any exemplary embodiment, the crosslinking agent may be present in the binder composition in an amount of 50 wt % to 85 wt %, based on the total solids content of the binder composition, including but not limited to 60 wt % to 82 wt %, 65 wt % to 80 wt %, and 68 wt % to 78 wt %, including all endpoints and subset combinations therebetween.

[0047] Surprisingly, it has been discovered that all or a percentage of the acid functionality in the polycarboxylic acid can be temporarily blocked by using a blocking agent that temporarily blocks the acid functionality from complexing with mineral wool fibers and is subsequently removed by heating the binder composition to a temperature of at least 150° C., releasing the acid functionality during the curing process to crosslink with the polyol component and complete the esterification process. In any exemplary embodiment, from 10% to 100% of the carboxylic acid functionality can be temporarily blocked by the blocking agent, including from about 25% to about 99%, from about 30% to about 90%, and from about 40% to 85%, including all subset ranges and range combinations therebetween. In any exemplary embodiment, at least 40% of the acid functionality can be temporarily blocked by the blocking agent.

[0048] The protective agent is capable of reversibly bonding to the carboxylic acid groups of the crosslinking agent. In any exemplary embodiment, the protective agent comprises any compound containing a molecule capable of forming at least one reversible ionic bond with a single acid functional group. In any exemplary embodiment disclosed herein, the protective agent may include a nitrogen-based protective agent, such as an ammonium-based protective agent; an amine-based protective agent; or a mixture thereof. Exemplary ammonium-based protective agents include ammonium hydroxide. Exemplary amine-based protective agents include alkylamines and diamines, such as ethyleneimine, ethylenediamine, hexamethylenediamine; alkanolamines, such as ethanolamine, diethanolamine, triethanolamine; ethylenediamine-N,N′-disuccinic acid (EDDS), ethylenediaminetetraacetic acid (EDTA), etc., or a mixture thereof. In addition, it has been surprisingly found that alkanolamines can be used both as protective agents and as participants in the crosslinking reaction to form esters in the cured binder. Therefore, alkanolamines have the dual functionality of a protective agent and a polyol for crosslinking with polycarboxylic acids by esterification.

[0049] like Figure 1 As shown, if left unprotected, the carboxylic acid groups in the polycarboxylic acid component will react with metal ions (Mg 2+ ,Al 3+ ,Ca 2+ ,Fe 3+ ,Fe 2+ ) forms a carboxylic acid-metal complex. In this case, when the binder composition is cured, the availability of the polyol and carboxylic acid groups for crosslinking is very limited, resulting in weak binder performance. On the contrary, Figure 2 The pre-reaction of a polycarboxylic acid with a nitrogen-based protective agent such as ammonium hydroxide or an amine is shown. This pre-reaction temporarily prevents the acid functional groups from permanently reacting with metal ions. When the binder cures, ammonia is released, freeing the acid functional groups to react with the polyol via esterification.

[0050] Surprisingly, the function of protective agent is different from conventional pH adjusting agent. Protective agent as defined in the present application only temporarily and reversibly blocks the acid functional group in the polymer polycarboxylic acid component. On the contrary, conventional pH adjusting agent (such as sodium hydroxide) permanently terminates the acid functional group, which prevents crosslinking between acid and hydroxyl due to the blocked acid functional group. Therefore, comprising traditional pH adjusting agent, such as sodium hydroxide, can not provide temporarily blocked acid functional group, and subsequently release these functional groups during curing to allow the desired effect of crosslinking through esterification. Therefore, in any exemplary embodiment disclosed in the present application, binder composition can be free of or substantially free of conventional pH adjusting agent, such as sodium hydroxide and potassium hydroxide. This conventional pH adjusting agent for high temperature applications will permanently bond with the carboxylic acid group and will not release the carboxylic acid functional group to allow crosslinking esterification.

[0051] Furthermore, in addition to providing a temporary seal, the protective agent also increases the pH of the binder composition to provide compatibility with the pH of the mineral wool fibers. If the pH of the binder composition is significantly lower than the pH of the fibers, the binder composition may damage the mineral fibers, altering their composition and weakening them. The binder composition's function is to bind the fibers together and should not react with the fibers themselves.

[0052] The pH of the binder composition in the uncured state can be adjusted according to the desired application to promote the compatibility of the ingredients of the binder composition, or to work with various types of fibers. In any exemplary embodiment disclosed herein, when in the uncured state, the binder composition has a pH of at least about 4. In such exemplary embodiments, when in the uncured state, the pH of the binder composition can be about 4.0-7.0, including about 4.2-6.8 and about 4.5-6.5. After curing, the pH of the binder composition can rise to a pH of at least 6.5 and a pH of at most 8.5. In any exemplary embodiment disclosed herein, the curing pH of the binder composition is 7.2 to 7.8.

[0053] The content of the protective agent in the binder composition can be 1.25wt% to 50.0wt%, based on the total solids in the binder composition, including but not limited to 2.50wt% to 25.0wt%, or 3.0wt% to 15.5wt%. In any exemplary embodiment disclosed herein, the protective agent is present in the binder composition with at least 3.5wt%, including at least 4.0wt%, at least 5.0wt%, at least 6.0wt% and at least 8.0wt%. In any exemplary embodiment, the protective agent can be used in an amount sufficient to block at least 40% of the acid functional groups of the polycarboxylic acid.

[0054] In any exemplary embodiment, the binder composition includes a ratio of carboxylic acid groups to amine groups of about 6:1 to about 1:1, or about 4:1 to about 1.5:1.

[0055] In any exemplary embodiment, the binder composition further includes at least one polyol having two or more hydroxyl groups (also referred to herein as a polyol). In any exemplary embodiment, the polyol comprises one or more of a monomeric or polymeric polyol.

[0056] Exemplary polyols include pentaerythritol, alkanolamines, mixtures thereof, or derivatives thereof. In any exemplary embodiment, the alkanolamine may include triethanolamine or a derivative thereof. Thus, in some exemplary embodiments, the polyol includes one or more of pentaerythritol, triethanolamine, derivatives thereof, or mixtures thereof.

[0057] In other exemplary embodiments, polyols may include one or more sugar alcohols. Sugar alcohols are understood to mean compounds obtained when the aldehyde or ketone groups of sugars are reduced (e.g., by hydrogenation) to corresponding hydroxyl groups. Starting sugars may be selected from monosaccharides, oligosaccharides, and polysaccharides, and mixtures of these products, such as syrups, molasses, and starch hydrolyzates. Starting sugars may also be dehydrated forms of sugars. Although sugar alcohols are very similar to corresponding starting sugars, they are not sugars. Therefore, for example, sugar alcohols do not have reducing power and cannot participate in the Maillard reaction typical of reducing sugars. In any exemplary embodiment, sugar alcohols include glycerol, erythritol, arabitol, xylitol, sorbitol, maltitol, mannitol, iditol, isomalt, lactitol, fiberbitol, palatinol, maltotriose, any one of their syrups and mixtures thereof. In various exemplary embodiments, sugar alcohols are selected from glycerol, sorbitol, xylitol, and mixtures thereof. In any exemplary embodiment, polyols may be dimerization or oligomerization condensation products of sugar alcohols. In any exemplary embodiment, the condensation product of the sugar alcohol can be isosorbide.In any exemplary embodiment, the sugar alcohol can be a diol or a dihydric alcohol.

[0058] In any exemplary embodiment, the binder composition may be free of reducing sugars. Reducing sugars are carbohydrates or sugars that contain free aldehyde or ketone groups and can donate electrons to another molecule. Because 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 binder composition with a brown color, which is undesirable for the present binder composition.

[0059] In any exemplary embodiments, polyol can include at least one natural origin and the carbohydrate derived from renewable resources.For example, carbohydrate can be derived from plant sources such as beans, maize, corn, glutinous corn, sugarcane, milo, white sorghum, potato, sweet potato, cassava (tapioca), rice, glutinous rice, pea, sago, wheat, oats, barley, rye, amaranth and / or cassava, and other plants with high starch content.Carbohydrate can also be derived from crude starch-containing products, and the crude starch-containing products are derived from the plant containing the residue of protein, polypeptide, lipid and low molecular weight carbohydrates.Carbohydrate can be selected from monosaccharide (for example wood sugar, glucose and fructose), disaccharides (for example sucrose, maltose and lactose), oligosaccharides (for example glucose syrup and fructose syrup) and polysaccharide and water-soluble polysaccharide (for example pectin, dextrin, maltodextrin, starch, modified starch and composition thereof).

[0060] The carbohydrate can be a carbohydrate polymer having a number average molecular weight of about 1,000 to about 8,000. Additionally, the carbohydrate polymer can have a dextrose equivalent (DE) number of 2 to 20, 7 to 11, or 9 to 14. In at least one exemplary embodiment, the carbohydrate is a water-soluble polysaccharide such as dextrin or maltodextrin.

[0061] The amount of polyol in binder composition can be up to about 50wt% total solids, includes but not limited to about 40wt%, about 35wt%, about 30wt%, about 28wt% and about 25wt% total solids at the most.In any exemplary embodiment, polyol can be present in binder composition with the amount of 5.0wt% to about 50wt% total solids, includes but not limited to 10wt% to 45wt%, 15wt% to 40wt%, 18wt% to 38wt%, 20wt% to 35wt%, 22wt% to 32wt%, 20wt% to 50wt% and 17wt% to 27wt% total solids, includes all endpoints and subset combinations therebetween.In any exemplary embodiment, polyol can provide 10: 1 to 0.2: 1, or 3: 1 to 0.5: 1 carboxylic acid group and the amount of the ratio of hydroxyl group exist.

[0062] Optionally, the binder composition may include an esterification catalyst, also referred to as a curing accelerator. The catalyst may include an inorganic salt, a Lewis acid (i.e., aluminum chloride or boron trifluoride), a Bronsted acid (i.e., sulfuric acid, p-toluenesulfonic acid, and boric acid), an organometallic complex (i.e., lithium carboxylate, sodium carboxylate), and / or a Lewis base (i.e., polyethyleneimine, diethylamine, or triethylamine). In addition, the catalyst may include an alkali metal salt of a phosphorus-containing organic acid; in particular, an alkali metal salt 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. In addition, 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. In addition, 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 catalysts.

[0063] The catalyst may be present in the binder composition in an amount of about 0% to about 10% by weight of the total solids in the binder composition, including but not limited to about 0 to about 5% by weight, or about 0.5% to about 4.5% by weight, or about 1.0% to about 4.0% by weight, or about 1.15% to about 3.8% by weight.

[0064] Optionally, the adhesive 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 adhesive composition in an amount of about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 2.5 wt %, about 0.05 wt % to about 1.5 wt %, or about 0.1 wt % to about 1.0 wt % of the total solids in the adhesive composition.

[0065] Non-limiting examples of silane coupling agents that can be used in the adhesive composition can be characterized by functional groups such as alkyl, aryl, amino, epoxy, vinyl, methacryloxy, ureido, isocyanato, and mercapto. In an exemplary embodiment, the silane coupling agent includes a silane containing one or more nitrogen atoms having one or more functional groups such as amine (primary, secondary, tertiary, and quaternary), amino, imino, amido, imide, ureido, or isocyanato. 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), methacryltrialkoxysilanes (e.g., 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane), hydrocarbon trialkoxysilanes, aminotrihydroxysilanes, epoxytrihydroxysilanes, methacryltrihydroxysilanes, and / or hydrocarbon trihydroxysilanes. In one or more exemplary embodiments, the silane is an aminosilane, such as γ-aminopropyltriethoxysilane.

[0066] Optionally, the binder composition may include one or more processing aids. There are no particular restrictions on the processing aids, as long as the processing aids serve to promote the processing of fiber formation and orientation. Processing aids can be used to improve the uniformity of binder application distribution, reduce binder viscosity, increase the slope height after forming, improve vertical weight distribution uniformity, and / or accelerate the dehydration of the binder during both forming and oven curing processes. Based on the total solids content in the binder composition, the processing aids can be present in the binder composition in an amount of 0 to about 15wt%, about 0.1wt% to about 10.0wt%, or about 0.3wt% to about 5.0wt%, or about 0.5wt% to 2.0wt%. In any exemplary embodiment, the aqueous binder composition may be substantially or completely free of any processing aids.

[0067] Examples of processing aids include defoamers, such as emulsions and / or dispersions of mineral, paraffin, or vegetable oils; dispersions of silicones, polydimethylsiloxane (PDMS) fluids, and silica that has been hydrophobized with polydimethylsiloxane or other materials. Other processing aids may include particles made from amide waxes such as ethylene bisstearamide (EBS) or hydrophobized silica.

[0068] Other processing aids may include viscosity modifiers including, for example, glycerol, 1,2,4-butanetriol, 1,4-butanediol, 1,2-propylene glycol, 1,3-propylene glycol, poly(ethylene glycol), and combinations thereof.

[0069] Another processing aid that can be used in the adhesive composition is a surfactant. One or more surfactants can be included in the adhesive composition to aid in adhesive atomization, wetting, and interfacial adhesion.

[0070] The surfactant is not particularly limited and includes surfactants such as, but 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 (sodium laureth sulfate); sulfate) and sodium myristyl ether 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., alkyl aryl ether phosphates and alkyl ether phosphates); carboxylates (e.g., alkyl carboxylates, fatty acid salts (soaps), sodium stearate, sodium lauroyl sarcosinate, carboxylate fluorosurfactants, perfluorononanoate, 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); and zwitterionic surfactants, quaternary ammonium salts (e.g., lauryltrimethylammonium chloride and alkylbenzyldimethylammonium chloride), polyoxyethylene alkylamines, and mixtures thereof.

[0071] Suitable nonionic surfactants that can be used in conjunction with the binder composition include polyethers (e.g., ethylene oxide and propylene oxide condensates, including linear and branched alkyl, and alkylaryl polyethylene glycol and polypropylene glycol ethers and thioethers); alkylphenoxypoly(ethyleneoxy)ethanols having an alkyl group containing from about 7 to about 18 carbon atoms and having from about 4 to about 240 ethyleneoxy units (e.g., heptylphenoxypoly(ethyleneoxy)ethanol and nonylphenoxypoly(ethyleneoxy)ethanol); polyoxyalkylene derivatives of hexitols including sorbitans, sorbitans, sorbic acid esters, mannide and dimannide; partial esters of long chain fatty acids (e.g., sorbitan monolaurate, sorbitan monopalmitate ... propylene oxide); ethylene oxide derivatives of long chain carboxylic acids, such as lauric, myristic, palmitic, and oleic acids, such as tall oil fatty acid; ethylene oxide derivatives of long chain alcohols, such as octanol, decanol, lauryl, or cetyl alcohol; and ethylene oxide / propylene oxide copolymers.

[0072] In any exemplary embodiment, the surfactant may include one or more of the following: Dynol 607 (which is 2,5,8,11-tetramethyl-6-dodecene-5,8-diol), 420, 440 and 465 (which is an ethoxylated 2,4,7,9-tetramethyl-5-decyn-4,7-diol surfactant (commercially available from Evonik Corporation, Allentown, Pa.)), Stanfax (sodium lauryl sulfate), Surfynol 465 (ethoxylated 2,4,7,9-tetramethyl-5-decyn-4,7-diol), Triton TM GR-PG70 (sodium 1,4-bis(2-ethylhexyl)sulfosuccinate) and Triton TM CF-10 (poly(oxy-1,2-ethanediyl), α-(phenylmethyl)-ω-(1,1,3,3-tetramethylbutyl)phenoxy).

[0073] The surfactant may be present in the binder composition in an amount of 0 to about 10 wt %, about 0.1 to about 5.0 wt %, or about 0.15 to about 2.0 wt %, or about 0.2 to 1.0 wt %, based on the total solids content of the binder composition.

[0074] Optionally, the binder composition may contain a dust suppressant to reduce or eliminate the presence of inorganic and / or organic particles that may have an adverse effect during the subsequent manufacture and installation of the insulation material. The dust suppressant may be any conventional mineral oil, mineral oil emulsion, natural or synthetic oil, bio-based oil, or lubricant, such as, but not limited to, silicone and silicone emulsions, polyethylene glycol, and any petroleum or non-petroleum oil with a high flash point to minimize evaporation of the oil within the oven.

[0075] In any exemplary embodiment, the binder composition may include up to about 10 wt % of a dust suppressant, including up to about 8 wt %, or up to about 6 wt %. In any exemplary embodiment, the binder composition may include 0 wt % to 10 wt % of a dust suppressant, including about 1.0 wt % to about 7.0 wt %, or about 1.5 wt % to about 6.5 wt %, or about 2.0 wt % to about 6.0 wt %, or about 2.5 wt % to 5.8 wt %.

[0076] Binder composition further comprises water for being applied on the fortifying fiber with dissolving or dispersion active solid.The amount of institute's added water is enough to be diluted to the viscosity that is suitable for it to be applied to fortifying fiber and on fiber, realizes the solid content of expectation with binder composition.Have been found that binder composition of the present invention can contain the solid content lower than traditional phenol-urea formaldehyde or carbohydrate-based binder composition.Especially, binder composition can comprise the binder solids of 3wt% to 35wt%, includes but not limited to the binder solids of 10wt% to 30wt%, 12wt% to 20wt% and 15wt% to 19wt%.

[0077] The binder content on the product can be measured as loss on ignition (LOI). In any exemplary embodiment, the LOI on the glass fibers forming the insulation product can be from 0.1% to 50%, including but not limited to 0.15% to 10%, 0.2% to 10%, and 0.3% to 5%.

[0078] In any exemplary embodiment, the binder composition can also include one or more additives, for example extender, cross-linking density reinforcing agent, deodorant, antioxidant, dust suppressant, biocide, moisture resistant agent or its combination.Optionally, binding agent can include but not limited to dyestuff, pigment, other filler, coloring agent, UV stabilizer, heat stabilizer, defoamer, emulsifying agent, preservative (for example sodium benzoate), corrosion inhibitor and composition thereof.Other additives can be added in the binder composition to improve technology and product performance.This type of additive comprises lubricant, wetting agent, antistatic agent and / or water-proofing agent.Additive can adopt the trace amount (for example<the about 0.1wt% of binder composition) of total solids from the binder composition until about 10wt% is present in the binder composition.

[0079] In any exemplary embodiment, the binder composition may be free or substantially free of a monomeric carboxylic acid component. Exemplary monomeric polycarboxylic acid components include aconitic acid, adipic acid, azelaic acid, butane tetracarboxylic acid dihydrate, butane tricarboxylic acid, chlorendic anhydride, citraconic acid, citric acid, dicyclopentadiene-maleic acid adduct, diethylenetriamine pentaacetic acid pentasodium salt, adduct of dipentene and maleic anhydride, endomethylene hexachlorophthalic anhydride, fully maleated rosin, maleated tall oil fatty acid, fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleated rosin - unsaturation oxidized with potassium peroxide to alcohols and then carboxylic acids, 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.

[0080] In any exemplary embodiment, the binder composition includes at least one crosslinking agent, a protective agent, a polyol, and has a pH of at least 4. Ranges for components used in the binder composition of the present invention according to certain exemplary embodiments are listed in Table 2. In embodiments including an alkanolamine as the polyol, the alkanolamine can also be considered an additional protective agent.

[0081] Table 2

[0082] Components Exemplary Range 1 (wt % Total Solids) Exemplary Range 2 (wt % Total Solids) crosslinking agent 50-80 53-75 Nitrogen-based protective agent 1.25-40.0 2.0-25.0 polyols 10-40* 15-30 COOH / N ratio 4:1 1.5:1

[0083] The binder compositions disclosed herein can be used to manufacture insulation products, such as mineral wool insulation products. Accordingly, aspects of the present inventive concept also relate to a method for producing a mineral wool product, comprising contacting mineral wool fibers with a binder composition as disclosed herein. The mineral wool product may include a facing on one or both major surfaces. The facing may be any type of facing substrate known in the art, such as a nonwoven mat, a foil mat, a polymeric surface mat, a woven fabric, and the like.

[0084] Figure 3 An exemplary method for producing a mineral wool product according to the present invention is depicted in FIG. A melt of raw mineral material is prepared in a reservoir 12, and a melt stream 14 is dropped into a spinning machine 16 (such as a centrifugal spinning machine), where the melt is fiberized and blown into a collection chamber 18 to form a mineral wool web on a collection belt 20. The binder composition can be applied to the mineral wool fibers before being collected on the collection belt, when the fibers are collected, or after the mineral wool web is formed. The binder composition can be applied to the mineral wool fibers in a known manner, such as by spraying. The binder-coated mineral wool web is then heated in a conventional curing oven to cure the binder-coated mineral wool web, thereby forming a mineral wool product. The mineral wool web can be subjected to compression to obtain the desired final product thickness.

[0085] Curing can be carried out in a curing oven at conventional temperatures, for example, from about 200°C to about 400°C, such as from about 225°C to about 350°C, and from about 230°C to about 300°C.

[0086] Mineral wool insulation products produced according to the present invention exhibit improved properties compared to mineral wool insulation products formed with otherwise identical binder compositions that do not include a protective agent. One such improved property includes tensile strength under hot and humid conditions (65°C / 95% relative humidity), both immediately upon manufacture and over extended periods of time. In any exemplary embodiment, the mineral wool insulation product according to the present invention may have a tensile strength of at least 30 kPa immediately upon manufacture and retain at least 50% of the tensile strength after 7 days under hot / humid conditions, including at least 53% tensile strength, at least 55% tensile strength, at least 58% tensile strength, and at least 60% tensile strength. In any exemplary embodiment disclosed herein, the mineral wool insulation product according to the present invention may have a tensile strength of 35 kPa-80 kPa immediately upon manufacture, including 38 kPa-75 kPa, and 42 kPa-70 kPa.

[0087] The mineral wool insulation products produced according to the present invention further exhibit improved compressive strength compared to mineral wool insulation products formed with an otherwise identical binder composition that does not include a protective agent. Compressive strength is measured and tested on samples using the standard EN 826 test method. Mineral wool insulation board products formed according to the present invention exhibit a compressive strength of at least 10 kPa, including at least 12 kPa and at least 13 kPa.

[0088] Having generally described the present invention, further understanding can be obtained by referring to certain specific embodiments shown below, which are provided for the purpose of implementing the present invention. Unless otherwise specified, these embodiments are only for illustration and are not intended to be all inclusive or limiting.

[0089] Example 1

[0090] Various exemplary polyacrylic acid-based adhesive composition premixes were prepared, wherein the polyacrylic acid polymer was chain-terminated with sodium hypophosphite to provide a number average molecular weight of 2000-5000. A protective agent was then added to the polyacrylic acid polymer to form an adhesive premix. The adhesive premix was diluted with water and included various additives as shown in Table 3 below to prepare the final adhesive composition. Each exemplary adhesive composition is listed below:

[0091] Table 3

[0092]

[0093] The binder composition described above was prepared and diluted to a solids concentration of approximately 12%. The binder composition was applied to the mineral wool using a typical mineral wool production line at a throughput of 4.5 tons / hour. Additional water was applied via an injection system to minimize fiber adhesion to the collection conveyor. The primary mineral wool layer was cross-lapped with additional mineral wool layers to produce approximately 50 kg / m2 of bonded material before the mineral wool board entered the curing oven. 3 The curing oven temperature was set at 250°C to 300°C. The final mineral wool board product was about 100 mm thick and had a density of about 55 kg / m 3 density.

[0094] Mineral wool board products were collected and subjected to a full range of standard tests. The results provided in Tables 3 and 4 illustrate the improved mineral wool product properties imparted by the binder composition of the present invention comprising a protective agent, compared to the product properties imparted by a similar acidic binder composition that does not include a protective agent. The test methods for each property are provided below.

[0095] Compressive strength at 10% strain Sample preparation and testing were performed using the standard EN 826 test method. The mineral wool board was 100 mm thick. The board was centered between the two plates of an Instron or equivalent compression testing instrument. The instrument compressed the sample until a strain of 10% was reached, providing the compressive stress at 10% strain. The compressive strength at 10% strain was calculated based on the following equation:

[0096] σ m =103·F m / A0[kPa]*

[0097] *F 10 = Force corresponding to -10% deformation [N]

[0098] F m = Maximum force [N]

[0099] A0=initial cross-sectional area [m 2 ].

[0100] Swelling (%): The swelling potential of the product is determined using a pressure cooker (or autoclave). This treatment complements the behavior of products stored in a hot box and can reveal product aging issues in a shorter time. In the pressure cooker, the product is stored at a pressure of 0.8-1 bar and 121°C for 15 minutes (autoclave at 2 bar and 134°C for 2.5 hours). The swelling (%) is the net increase in volume after treatment in the pressure cooker (or autoclave).

[0101] Tensile strength in Y direction (EN 1607) : Sample products measuring 100 mm x 100 mm in the Y direction were prepared and the plywood was glued at both ends in the machine Y direction. The samples were attached to a tensile testing fixture, and the maximum force was recorded as the tensile strength. Sample products were tested: 1) at the end of the line (EOL), 2) after one day in a hot box, 3) for seven days, and 4) after aging and heat / humidity conditioning for 28 days before tensile testing. Conditions in the hot box included a temperature of 65°C and 95% relative humidity. The tensile retention percentage after 28 days in the hot box is reported as Res% (the elongation after 28 days divided by the elongation at the end of the line).

[0102] As illustrated in Tables 4 and 5 below, comprising a protective agent with at least 40% protected COOH group provides significant impact on product performance. Embodiment 1-3 each comprises at least 40% COONH4 group, shows that at least 40% COOH group is temporarily closed by the protective agent of nitrogen group, and each embodiment demonstrates at least 12.0kPa compressive strength and less than 1% swelling. In addition, each among the embodiments 1-3 keeps more than 20% tensile strength after 28 days under heat / humidity conditions. When not comprising the nitrogen group protective agent, comparative example 1-3 shows 2.0% or higher swelling and loses significant tensile strength, and breaks after 28 days under heat / humidity conditions in some cases. In addition, the comparative example 3 that comprises regulating pH with sodium hydroxide shows the highest swelling incidence (11.3%), and only breaks after 1 day under heat / humidity conditions. Therefore, it is obvious that traditional pH regulation can not realize the protective function that protective agent provides this binder composition.

[0103] Table 4

[0104]

[0105] Table 5

[0106]

[0107] It will be understood that many of the more detailed aspects of the products and methods shown are largely known in the art and have been omitted for the purpose of concisely presenting the overall inventive concept. Although the invention has been described with reference to specific devices, materials, and embodiments, from the foregoing description, one skilled in the art can readily ascertain the essential characteristics of the present invention and that various changes and modifications may be made to accommodate various uses and features without departing from the spirit and scope of the invention as described above and set forth in the appended claims.

[0108] The following paragraphs provide further exemplary embodiments.

[0109] Paragraph 1. A method of manufacturing an insulation product, comprising:

[0110] collecting a plurality of inorganic fibers on a substrate, the inorganic fibers formed from a composition comprising at least 25 weight percent divalent and trivalent metal oxides;

[0111] An aqueous binder composition is applied to the collection of inorganic fibers to form binder-coated inorganic fibers, the aqueous binder composition comprising:

[0112] at least 50 wt% solids of a cross-linking agent comprising at least two carboxylic acid groups;

[0113] 10.0-40.0 wt% solids of a polyol component having at least two hydroxyl groups;

[0114] 1.25-50.0 wt% solid nitrogen-based protective agent, wherein the nitrogen-based protective agent comprises at least one of an amine-based protective agent or an ammonium-based protective agent and temporarily blocks at least 40% of the carboxylic acid groups of the cross-linking agent;

[0115] removing the nitrogen-based protective agent by heating the binder-coated inorganic fibers to a temperature of at least 150° C.; and

[0116] The aqueous binder composition is cured by an esterification reaction between the crosslinking agent and the polyhydroxy component to form an inorganic fibrous insulation product, wherein the aqueous binder composition is free of added formaldehyde.

[0117] Paragraph 2. The method of Paragraph 1, wherein the crosslinking agent is present in the binder composition in an amount of 55 wt% to 85 wt% solids based on the total solids content of the aqueous binder composition.

[0118] Paragraph 3. The method according to paragraph 1 or paragraph 2, wherein the polyol component comprises a sugar alcohol, an alkanolamine, pentaerythritol, or a mixture thereof.

[0119] Paragraph 4. The method of any of paragraphs 1 to 3, wherein the nitrogen-based protecting agent comprises ethylenediamine, ammonium hydroxide, ethylenediaminetetraacetic acid, or a mixture thereof.

[0120] Paragraph 5. The method of any of Paragraphs 1 to 4, wherein the aqueous binder composition has an uncured pH of 4.0 to 7.0.

[0121] Paragraph 6. The method of any of Paragraphs 1 to 5, wherein the aqueous binder composition has an uncured pH of 4.2 to 6.5.

[0122] Paragraph 7. The method according to any of paragraphs 1 to 6, wherein the insulation product has a longitudinal tensile strength according to EN 1607 of at least 30 kPa immediately after manufacture.

[0123] Paragraph 8. The method of Paragraph 7, wherein the insulation product retains at least 50% of its tensile strength after 7 days in a tropical cabinet at a temperature of 65°C and 95% relative humidity.

[0124] Paragraph 9. The method of Paragraph 7 or Paragraph 8, wherein the insulation product retains at least 60% of its tensile strength after 7 days in a tropical oven at a temperature of 65°C and 95% relative humidity.

[0125] Paragraph 10. The method of any of paragraphs 1 to 9, wherein the insulation product has a compressive strength at 10% strain of at least 10 kPa according to EN 826.

[0126] Paragraph 11. A fiber product comprising:

[0127] a plurality of randomly oriented mineral wool fibers; and

[0128] An ester cross-linked thermosetting binder composition at least partially coating the fibers, wherein prior to cross-linking, the binder composition comprises an aqueous composition comprising the following components:

[0129] at least 50 wt% solids of a cross-linking agent comprising at least two carboxylic acid groups;

[0130] 10.0-40.0 wt. % solids of at least one polyol having at least two hydroxyl groups, based on the total solids content of the aqueous binder composition; and

[0131] 1.25-50.0 wt% solid nitrogen-based protective agent, wherein the nitrogen-based protective agent comprises at least one of an amine-based protective agent or an ammonium-based protective agent;

[0132] Prior to cross-linking, the nitrogen-based protective agent temporarily blocks at least 40% of the carboxylic acid groups of the cross-linking agent;

[0133] The mineral wool insulation product has a longitudinal tensile strength according to EN 1607 of at least 30 kPa immediately upon manufacture and retains at least 50% of the tensile strength after 7 days under hot / humid conditions.

[0134] Paragraph 12. The fibrous product of Paragraph 11, wherein the fibrous product comprises any one of an insulation product, a nonwoven mat, a particle board, a ceiling panel, and a duct panel.

[0135] Paragraph 13. The fiber product of paragraph 11 or paragraph 12, wherein the fiber product retains at least 60% of its tensile strength after 7 days in a tropical oven at a temperature of 65°C and 95% relative humidity.

[0136] Paragraph 14. The fiber product of any of paragraphs 11 to 13, wherein the crosslinking agent is present in the binder composition in an amount of 60 to 82 wt % based on the total solids content of the aqueous composition.

[0137] Paragraph 15. The fiber product of any of Paragraphs 11 to 14, wherein the polyol component comprises a sugar alcohol, an alkanolamine, pentaerythritol, or a mixture thereof.

[0138] Paragraph 16. The fiber product of any of paragraphs 11 to 15, wherein the polyol component comprises sorbitol, triethanolamine, pentaerythritol, or a mixture thereof.

[0139] Paragraph 17. The fibrous product of any of paragraphs 11 to 16, wherein the fibrous product has a compressive strength at 10% strain according to EN 826 of at least 10 kPa.

[0140] Paragraph 18. An aqueous binder composition comprising:

[0141] at least 50 wt% solids of a polymeric crosslinker comprising at least two carboxylic acid groups;

[0142] at least 8.0 wt% solids of a nitrogen-based protective agent; and

[0143] 10.0-35.0 wt% solids of at least one polyol component having at least two hydroxyl groups; wherein the binder composition has a ratio of crosslinker to nitrogen-based protective agent of 4:1 to 1.5:1 and an uncured pH of at least 4.5,

[0144] Before curing the adhesive composition, at least 40% of the carboxylic acid groups are temporarily blocked by the nitrogen-based protective agent.

[0145] Paragraph 19. The aqueous binder composition of Paragraph 18, wherein the crosslinking agent is present in the aqueous binder composition in an amount of 60-82 wt % based on the total solid content of the aqueous binder composition.

[0146] Paragraph 20. The aqueous binder composition of Paragraph 18 or Paragraph 19, wherein the polyol component comprises one or more of a sugar alcohol, an alkanolamine, pentaerythritol, or a mixture thereof.

[0147] Paragraph 21. The aqueous binder composition of any of paragraphs 18-20, wherein the polyol component comprises sorbitol, triethanolamine, pentaerythritol, or a mixture thereof.

[0148] Paragraph 22. The aqueous binder composition of any of Paragraphs 18-21, wherein the nitrogen-based protective agent is an amine-based protective agent or ammonium hydroxide.

Claims

1. A method for manufacturing an insulation product, comprising: collecting a plurality of inorganic fibers on a substrate, the inorganic fibers formed from a composition comprising at least 25 weight percent divalent and trivalent metal oxides; An aqueous binder composition is applied to the assembly of inorganic fibers to form binder-coated inorganic fibers, the aqueous binder composition comprising, based on 100 wt% of the total solids content of the aqueous binder composition: at least 50 wt % of a cross-linking agent comprising at least two carboxylic acid groups, wherein the cross-linking agent is selected from at least one of a monomeric polycarboxylic acid, an acrylic acid homopolymer, and an acrylic acid copolymer; 10.0 to 40.0 wt% of a polyol component having at least two hydroxyl groups; 1.25-50.0 wt% of a nitrogen-based protective agent, wherein the nitrogen-based protective agent comprises at least one of an amine-based protective agent or an ammonium-based protective agent and temporarily blocks at least 40% of the carboxylic acid groups of the cross-linking agent; removing the nitrogen-based protective agent by heating the binder-coated inorganic fibers to a temperature of at least 150° C.; as well as The aqueous binder composition is cured by an esterification reaction between the crosslinking agent and the polyol component to form an inorganic fibrous insulation product, wherein the aqueous binder composition is free of added formaldehyde. 2 . The method according to claim 1 , wherein the crosslinking agent is present in the binder composition in an amount of 55 wt % to 85 wt % based on 100 wt % of the total solid content of the aqueous binder composition.

3. The method according to claim 1, wherein the polyol component comprises at least one of sugar alcohol, alkanolamine, and pentaerythritol.

4. The method according to claim 1, wherein the nitrogen-based protective agent comprises at least one of ethylenediamine and ammonium hydroxide.

5. The method according to claim 1, wherein the aqueous binder composition has an uncured pH of 4.0 to 7.

0.

6. The method according to claim 1, wherein the aqueous binder composition has an uncured pH of 4.2 to 6.

5.

7. The method of claim 1, wherein the insulation product immediately upon manufacture has a longitudinal tensile strength according to EN 1607 of at least 30 kPa.

8. The method of claim 7, wherein the insulation product retains at least 50% of its tensile strength after 7 days in a tropical cabinet at a temperature of 65°C and a relative humidity of 95%.

9. The method of claim 7, wherein the insulation product retains at least 60% of its tensile strength after 7 days in a tropical oven at a temperature of 65°C and a relative humidity of 95%.

10. The method of claim 1, wherein the insulation product has a compressive strength of at least 10 kPa at 10% strain according to EN 826.

11. A fiber product comprising: a plurality of randomly oriented mineral wool fibers; and An ester cross-linked thermosetting binder composition that at least partially coats the fibers, wherein before cross-linking, the binder composition comprises an aqueous composition comprising the following components, based on 100 wt % of the total solids content of the binder composition: at least 50 wt % of a cross-linking agent comprising at least two carboxylic acid groups, wherein the cross-linking agent is selected from at least one of a monomeric polycarboxylic acid, an acrylic acid homopolymer, and an acrylic acid copolymer; 10.0 to 40.0 wt% of at least one polyol component having at least two hydroxyl groups; and 1.25 to 50.0 wt % of a nitrogen-based protective agent, wherein the nitrogen-based protective agent comprises at least one of an amine-based protective agent or an ammonium-based protective agent; Prior to crosslinking, the nitrogen-based protecting agent temporarily blocks at least 40% of the carboxylic acid groups of the crosslinking agent; Wherein the fiber product comprises a mineral wool insulation product having a longitudinal tensile strength according to EN 1607 of at least 30 kPa immediately upon manufacture and retaining at least 50% of the tensile strength after 7 days under hot / humid conditions.

12. The fiber product according to claim 11, wherein the mineral wool insulation product retains at least 60% of its tensile strength after 7 days in a tropical cabinet at a temperature of 65°C and a relative humidity of 95%. 13 . The fiber product according to claim 11 , wherein the crosslinking agent is present in the binder composition in an amount of 60 wt % to 82 wt % based on the total solid content 100 wt % of the binder composition.

14. The fiber product according to claim 11, wherein the polyol component comprises at least one of sugar alcohol, alkanolamine, and pentaerythritol.

15. The fiber product according to claim 14, wherein the polyol component comprises at least one of sorbitol, triethanolamine, and pentaerythritol.

16. The fiber product according to claim 11, wherein the mineral wool insulation product has a compressive strength of at least 10 kPa at 10% strain according to EN 826.

17. An aqueous binder composition, comprising, based on 100 wt % of the total solid content of the aqueous binder composition: At least 50 wt% of a polymer cross-linking agent comprising at least two carboxylic acid groups, wherein the cross-linking agent is selected from at least one of an acrylic acid homopolymer and an acrylic acid copolymer; at least 8.0 wt% of a nitrogen-based protective agent; and 10.0 to 35.0 wt% of at least one polyol component having at least two hydroxyl groups; wherein the binder composition has a ratio of crosslinker to nitrogen-based protective agent of 1.5:1 to 4:1 and an uncured pH of at least 4.5, Before curing the adhesive composition, at least 40% of the carboxylic acid groups are temporarily blocked by the nitrogen-based protective agent. 18 . The aqueous binder composition according to claim 17 , wherein the crosslinking agent is present in the aqueous binder composition in an amount of 60 wt % to 82 wt % based on 100 wt % of the total solid content of the aqueous binder composition.

19. The aqueous binder composition according to claim 17, wherein the polyol component comprises at least one of sugar alcohol, alkanolamine, and pentaerythritol.

20. The aqueous binder composition according to claim 19, wherein the polyol component comprises at least one of sorbitol, triethanolamine, and pentaerythritol.

21. The aqueous binder composition according to claim 17, wherein the nitrogen-based protective agent is an amine-based protective agent or ammonium hydroxide.

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