Mineral fibre products

Abstract

A method of manufacturing a mineral fibre product, i.e. non-woven mineral fibre veil, mineral wool insulation, glass or stone wool insulation, may comprise applying an aqueous, curable binder composit

Description

[0001] The present invention relates to mineral fibre products, notably non-woven mineral fibre veils, mineral wool insulation, glass wool insulation and stone wool insulation, to a method for their production, and particularly to curable binder compositions for these products.

[0002] The mineral wool industry has historically used phenol formaldehyde binders, particularly urea extended phenol formaldehyde binders, to bind mineral wool fibres. Phenol formaldehyde type binders provide a desirable combination of properties; however, environmental considerations have motivated the development of alternative binders, notably binders referred to as no added formaldehyde binders because these binders do not utilize formaldehyde as a reagent. For example non phenol formaldehyde binders are disclosed in the following patent applications: WO03 / 104284 discloses binders comprising the reaction products of an epoxide and an epoxide crosslinking agent; WO2005 / 087837 discloses binders comprising the esterification products of reacting a polycarboxylic acid and a polyol; WO2012 / 118939 discloses binders comprising esterification products of carbohydrates and polycarboxylic acids; WO2004 / 007615 discloses binder comprising reacting carbohydrate with reaction products of alkanolamine and carboxylic anhydride; WO 2007 / 014236 discloses carbohydrate based binder that comprises a Maillard reaction product, notably a carbohydrate based binder derived from reacting a reducing sugar, a carboxylic acid and ammonia; WO 2009 / 019235 discloses carbohydrate based binder derived from reacting a reducing sugar and an acid precursor derived from an inorganic salt, in particular an ammonium salt; WO2012 / 072938 discloses binders derived from reacting non-reducing sugars and inorganic-acid ammonium salts, WO2011 / 138458 discloses carbohydrate based binder comprising the reaction products of a carbohydrate reactant and a polyamine.

[0003] Despite the numerous propositions for and the benefits of no added formaldehyde binders, urea extended phenol formaldehyde binders are still the industry standard binders for mineral wool insulation. Consequently, it would be desirable to make further improvements in no added formaldehyde binder compositions to provide a desirable combination of properties that would lead to wider use. Notably, it would be desirable to make improvements to enhance environmental considerations and enhance the working conditions in the plant. Notably it would be desirable to make further improvements in no added formaldehyde binder compositions to provide a desirable combination of properties while reducing the ammonia emissions on the manufacturing line (where environmental control is difficult to implement) and / or from curing oven flue gasses (which commonly require environmental control or purification prior to release).

[0004] In accordance with one aspect, the present invention provides a method of manufacturing a mineral fibre product selected from a non-woven mineral fibre veil, mineral wool insulation, glass wool insulation and stone wool insulation, the method comprising: - applying an aqueous, curable binder composition to non or loosely assembled mineral fibres to provide resinated mineral fibres; and - subjecting the resinated mineral fibres to heat to cure the aqueous, curable binder composition and to form the mineral fibre product; - wherein the aqueous, curable binder composition applied to the mineral fibres comprises: 1) reducing sugar(s), 2) inorganic ammonium salt(s), wherein the inorganic ammonium salt consists of ammonium sulfate (NH4)2SO4, 3) organic amine(s) having a pka of 7.5 or more and of 9.0 or less, wherein the organic amine(s) is selected from the group consisting of triethanolamine, diethanolamine, morpholine and combinations thereof; and 4) optional additive(s), notably silane coupling agent(s) and wherein when (a) represents the total dry weight of the reducing sugar(s), (b) represents the total dry weight of the inorganic ammonium salt(s), and (c) represents the total dry weight of the organic amine(s), (a) + (b) + (c) is at least 90 wt% of the total dry weight of the aqueous, curable binder composition; (a) is 60 to 90 wt % of the total dry weight of (a), (b) and (c); (b) is 2.5 to 25 wt % of the total dry weight of (a), (b) and (c); and (c) is 0.2 to 2 wt % of the total dry weight of (a), (b) and (c).

[0005] The present invention provides binder compositions with properties including excellent curing rates, bond strength, parting strength, tensile strength and low swelling properties, ease of handling and good storage stability. Notably, the present aqueous, curable binder composition provides the desirable bond strength and fire resistance properties of mineral fibre product obtained with aqueous, curable binder composition in accordance with WO 2009 / 019235 while providing reduced ammonia emissions; this is achieved with the defined low quantity of organic amine(s) having a pka of 7.5 or more and of 9.0 or less instead of the additional ammonia used as pH buffering in the curable binder composition in accordance with WO 2009 / 019235.

[0006] The non or loosely assembled mineral fibres matter may comprise woven or non-woven fibre material. The mineral fibres may be selected from stone wool fibres, glass fibres and combinations thereof.

[0007] The mineral fibre product may be mineral fibre insulation product, for example glass wool insulation or stone wool insulation. The mineral fibre products may be mineral fibre veil, e.g. a glass fibre veil, which may then find application for example in battery separators, as substrate for roofing products such as roofing membranes or shingles, or other membranes.

[0008] Any feature described herein in relation to a particular aspect of the invention may be used in relation to any other aspect of the invention.

[0009] The term “aqueous, curable binder composition” as used herein means all binder ingredients applied to the non or loosely assembled mineral fibres and / or present on the non or loosely assembled mineral fibres, notably prior to curing, (other than the non or loosely assembled mineral fibres itself and any moisture in the non or loosely assembled mineral fibres), including reactants, solvents (including water) and additives. The term “dry weight of the aqueous, curable binder composition” as used herein means the weight of all components of the aqueous, curable binder composition other than any water that is present (whether in the form of liquid water or in the form of water of crystallization).

[0010] The aqueous, curable binder composition applied to the non or loosely assembled mineral fibres comprises reactants which cross-link when cured to form a cured binder which holds the non or loosely assembled matter together to form the mineral fibre product. The aqueous, curable binder composition comprises reactants that will preferably form a thermoset resin upon curing. The cured aqueous, curable binder composition is preferably a thermoset resin. The reactants of the aqueous, curable binder composition comprise, preferably consist essentially of, and more preferably consist of 1) the reducing sugar(s), and 2) the inorganic ammonium salt(s).

[0011] The aqueous, curable binder composition is preferably a “no added formaldehyde binder”, that is to say that it does not comprise formaldehyde as a binder reagent. It may be substantially formaldehyde free; as used herein the term “substantially formaldehyde free” means that the aqueous, curable binder composition liberates less than 5 ppm formaldehyde as a result of drying and / or curing (or appropriate tests simulating drying and / or curing); more preferably it is formaldehyde free, as used herein the term “formaldehyde free” means that the aqueous, curable binder composition liberates less than 1 ppm formaldehyde in such conditions.

[0012] Preferably, the aqueous, curable binder composition is a reducing sugar based binder composition; as used herein the term “reducing sugar based binder composition” means that the aqueous, curable binder composition comprises at least 50 wt% of reducing sugar(s) by dry weight based on the total dry weight of the aqueous, curable binder composition.

[0013] As used herein, the term "consist or consisting essentially of is intended to limit the scope of a statement or claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the invention.

[0014] The reducing sugar(s) may comprise: a monosaccharide, a monosaccharide in its aldose or ketose form, a disaccharide, a polysaccharide, a triose, a tetrose, a pentose, xylose, a hexose, dextrose, fructose, a heptose, or mixtures thereof. The reducing sugar(s) may comprise, consist essentially of, or consist of a combination of dextrose and fructose, for example in which the combination of dextrose and fructose makes up at least 80 wt% of the reducing sugar(s) and / or in which the dextrose makes up at least 40 wt% of the reducing sugar(s) and / or in which the fructose makes up at least 40 wt% of the reducing sugar(s); the reducing sugar reactant(s) may comprise, consist essentially of, or consist of high fructose corn syrup (HFCS). The reducing sugar reactant(s) may be derived from carbohydrate reactant(s), notably carbohydrate reactant(s) having a dextrose equivalent of at least about 50, at least about 60, at least about 70, at least about 80 or at least about 90, notably carbohydrate reactant(s) selected from the group consisting of molasses, starch, starch hydrolysate, cellulose hydrolysates, and mixtures thereof. The reducing sugar reactant(s) may be derived from hemicellulose. The reducing sugar(s) may be derived from non-reducing sugar(s) that yield the reducing sugar(s) in situ, notably sucrose. The reducing sugar(s) may comprise reducing sugar(s) selected from the group consisting of xylose, arabinose, dextrose, mannose, fructose and combinations thereof, for example making up at least 80 wt% of the reducing sugar(s). The reducing sugar(s) may comprise reducing sugar(s) selected from the group consisting of xylose, arabinose, dextrose, mannose, fructose, galactose and combinations thereof.

[0015] The inorganic ammonium salt(s) consist of ammonium sulfate (NH4)2SO4. When introduced into aqueous solutions, the inorganic ammonium salts provide the corresponding ions, i.e. when introduced into water, ammonium sulfate (NH4)2SO4 provides the corresponding ammonium and sulfate ions.

[0016] The organic amine(s) of the present invention have a pka of 7.5 or more and of 9.0 or less. As used herein pKa is the acid dissociation constant. Unless otherwise specified, pKa is measured in water at 25°C. As used herein the "pKa" of an organic amine will be treated as the pKa of the most acidic proton of the organic amine or the lowest pKa of the organic amine, i.e. the pKa of the strongest proton or base conjugate is understood.

[0017] The organic amine(s) comprise a secondary amine or a tertiary amine group. The organic amine(s) comprise a hydroxyl or ether function. The organic amine(s) comprise both a secondary amine or a tertiary amine and a hydroxyl or ether function. The organic amine is a monoamine, i.e. it comprises one and only one amine function.

[0018] The organic amine(s) comprise, more preferably consist essentially of, and most preferably consist of compound(s) selected from the group consisting of triethanolamine, diethanolamine, morpholine and combinations thereof. In one embodiment, the organic amine consists of triethanolamine. In another embodiment, the organic amine consists of diethanolamine. In another embodiment, the organic amine consists of morpholine.

[0019] The organic amine(s) may be added to provide a pH of the aqueous binder solution of between about 7-9, preferably a pH of about 8.

[0020] The aqueous, curable binder composition may be prepared by combining compounds comprising, preferably consisting essentially of, and more preferably consisting of the 1) reducing sugar(s), 2) inorganic ammonium salt(s), 3) organic amine(s), and 4) optional additive(s), notably an optional silane coupling agent.

[0021] The aqueous curable binder composition may be devoid of organic acids, notably devoid of polycarboxylic acid(s).

[0022] When (a) represents the total dry weight of the reducing sugar(s), (b) represents the total dry weight of the inorganic ammonium salt(s), (c) represents the total dry weight of the organic amine(s), - (a) represents from 60 wt% to 90 wt%, preferably from 65 wt% to 90 wt%, more preferably from 70 wt% to 90 wt%, more preferably from 75 wt% to 90 wt%, even more preferably from 75 wt% to 85 wt% of the total dry weight of (a), (b) and (c); - (b) represents from 2.5 wt% to 25 wt%, preferably from 2.5 wt% to 20 wt%, more preferably from 5 wt% to 20 wt % of the total dry weight of (a), (b) and (c); - (c) represents from 0.2 wt% to 2 wt%, preferably from 0.5 wt% to 2 wt%, more preferably from 0.5 wt% to 1.0 wt% of the total dry weight of (a), (b) and (c); - (a) + (b) + (c) is at least 90 wt%, preferably 95 wt%, more preferably at least 97 wt%, even more preferably at least 98 wt% of the total dry weight of the aqueous, curable binder composition.

[0023] Curing of the aqueous, curable binder composition may comprise Maillard reaction(s). The cured binder composition may comprise melanoidin-containing and / or nitrogenous-containing polymer(s). The cured binder composition is preferably a thermoset binder. The cured binder composition is preferably substantially water insoluble. Curing of the aqueous, curable binder composition may involve condensation reactions, elimination reactions, addition polymerization reactions, ionic interactions, or electrostatic interactions between one or more of the reactants.

[0024] The aqueous, curable binder composition may comprise 4) optional additive(s), for example one or more additives selected from dedusting oil, waxes, water repellent agent, silanes and silicones. When (d) represents the total dry weight of the optional additive(s), (d) is less than 10 wt%, less than 8 wt%, preferably less than 5 wt%, more preferably less than 3 wt%, of the total dry weight of the aqueous, curable binder composition.

[0025] The optional additive(s) may comprise optional silane coupling agent(s), notably epoxysilane(s) and / or aminosilane(s). When manufacturing mineral fibre products, silane coupling agent(s) are used to enhance the adhesion of the binder composition to the mineral fibres. The silane coupling agent(s) comprise a silane group able to react with silanol groups at a surface of the mineral fibres, and at least one reactive function, notably amine or oxirane able to react with the binder composition. Preferably the optional silane coupling agent(s) (when used) comprise, consist essentially of, or consist of aminosilane(s). The total dry weight of the optional silane coupling agent(s) when used may be less than 2 wt%, preferably less than 1 wt%, and more than 0.1 wt%, preferably more than 0.3 wt% of the total dry weight of the aqueous curable binder composition.

[0026] The dry weight of the aqueous, curable binder composition when applied to the non or loosely assembled mineral fibres as an aqueous solution or dispersion, may makes up: >5 wt%, >10 wt%, >15 wt%, >20 wt% or >25 wt and / or <95 wt%, <90 wt%, <85 wt% or <80 wt% of the total weight of the aqueous, curable binder composition. The aqueous, curable binder composition may be applied by being sprayed. The aqueous, curable binder composition may be applied to the non or loosely assembled mineral fibres by passing the non or loosely assembled mineral fibres through a spray of the aqueous, curable binder composition or by spraying the aqueous, curable binder composition over the non or loosely assembled mineral fibres.

[0027] In one aspect, the aqueous, curable binder composition may be used to make mineral wool insulation products. The method of producing a mineral wool insulation product may comprise the sequential steps of: - forming a mineral melt from a molten mineral mixture - forming mineral fibres from the mineral melt - spraying the aqueous, curable binder composition on to the mineral fibres, notably spraying the aqueous, curable binder composition on to airborne mineral fibres subsequent to formation of the fibres and prior to collection of the fibres to form a blanket of mineral fibres; - collecting the mineral fibres to which the aqueous, curable binder composition has been applied to form a blanket of mineral fibres; and - curing the aqueous, curable binder composition by passing the blanket of mineral fibres through a curing oven.

[0028] Prior to curing, the mineral fibres to which the aqueous, curable binder composition has been applied may be collected to form a primary blanket of mineral fibres which is subsequently folded over itself, for example using a pendulum mechanism, to produce a secondary blanket comprising superimposed layers of the primary blanket.

[0029] The dry weight of the aqueous, curable binder composition, notably when applied to the mineral fibres, may make up from 5 wt% to 20 wt%, preferably from 7.5 wt% to 18 wt%, more preferably from 10 wt% to 15 wt%, even more preferably from 12 wt% to 15 wt% of the total weight ofthe aqueous, curable binder composition.

[0030] The curing oven may have a plurality of heating zones having temperatures within the range 200 °C to 350 °C (typically 230°C to 300 °C). A thin, low density product (12 kg / m3 or less) may be cured by passing through the curing oven in as little as 20 seconds; a thick, high density product (80 kg / m3 or more) may require a passage of 15 minutes or more in the curing oven. The blanket of mineral fibres may reach a temperature in the range 180 °C - 220 °C during the curing process. The duration of passage ofthe blanket through the curing oven may be >0.5 minutes, >1 minute, >2 minutes, >5 minutes or >10 minutes and / or <50 minutes, <40 minutes or <30 minutes.

[0031] The quantity of cured binder in the cured blanket of mineral fibres may be >1%, >2%, >2.5%, >3%, >3.5% or> 4% and / or <10% or< 8%. This may be measured by loss on ignition (LOI).

[0032] The mineral fibre product may have a density which is greater than 5, 8 or 10 kg / m3 and less than 200, 180 or 150 km / m3. The mineral fibre product may be a glass wool insulation product having a density greater than 5, 6, 8 or 10 kg / m3 and less than 125, 80, 60 or 50 kg / m3; it may be a stone wool insulation product having a density greater than 15, 20 or 25 kg / m3 and less than 220, 200 or 180 kg / m3. Such mineral fibre products may: have a thermal conductivity A of less than 0.05 W / mK and greater than 0.02 W / mK measured at 10°C notably in accordance with EN12667; comprise less than 99% by weight and more than 80% by weight mineral fibres; have a thickness of greater than 10 mm, 15mm or 20 mm and less than 400mm, 350 mm or 300 mm. Preferably, such mineral fibre products have, in combination, the aforementioned thermal conductivity A, % weight mineral fibres and thickness.

[0033] The mineral fibre insulation product, notably when it is a low or medium density mineral fibre insulation product, may have - a nominal thickness in the range 60-260mm; and / or - a thermal resistance R of R> 3 m2K / W, preferably R> 4 m2K / W at a thickness or 200mm; and / or a density in the range 5-40 kg / m3, particularly 5-18 kg / m3 or 7-12 kg / m3.

[0034] The mineral fibre insulation product, notably when it is a high density mineral fibre insulation product, may have - a nominal thickness in the range 20 to 200 mm; and / or - a thermal resistance R of R>1.7 m2K / W, preferably R>2 m2K / W at a thickness or 100mm; and / or - a density in the range 100 to 200 kg / m3, particularly 130 to 190 kg / m3.

[0035] According to one aspect, the aqueous, curable binder composition may be used to make a non-woven mineral fibre veil. The non-woven mineral fibre veil may be manufactured by a wet laid process or a dry laid process. The method of producing the non-woven mineral fibre veil may comprise the sequential steps of: - forming a mineral fibre web, notably the mineral fibre web may be formed by i) pouring a dispersion of fibres in water, notably chopped mineral fibres, on to a perforated conveyor belt (often referred to as a wire) through which the water is drained to form a non-woven web of fibres or ii) projecting fibres in an airstream towards of perforated conveyor to form a web of non-woven fibres - applying the aqueous, curable binder composition on to the mineral fibres, notably by coating the aqueous, curable binder composition on to the mineral fibre web; and - curing the aqueous, curable binder composition by passing the resinated mineral fibre web through a curing oven.

[0036] When the product is a non-woven mineral fibre veil, the quantity of cured binder in the final product may be >1%, >2.5%, >5%, >7.5% >10 %, or> 12.5 % and / or< 25%, <22.5%, <20% or< 17.5%. This may be measured by loss on ignition (LOI).

[0037] The thickness of the non-woven mineral fibre veil may be >0.1 mm or >0.3 mm and / or <0.8 mm or <0.6 mm. When the non-woven mineral fibre veil is a glass veil, the thickness may be >0.3 mm and <0.6 mm. The non-woven mineral fibre veil may have a surface weight >20 g / m2 or >30 g / m2 or >40 g / m2 or >50 g / m2 and / or <60 g / m2 or <80 g / m2 or <100 g / m2 or <150g / m2 or <350 g / m2.

[0038] Methods of manufacturing mineral fibre products according to the present invention allow for cure speeds which are at least equivalent to and indeed fasterthan those obtained with comparable binder systems; similarly, the dry and wet tensile strengths of the cured mineral fibre products is at least equivalent to that obtained with comparable binder systems.

[0039] The use of the organic amines provides several benefits in addition to reduced ammonia emission in plant and thus enhancing environmental concerns. Compared to NH3 aq, the organic amines are easier to handle, particularly in an industrial environment. Also, the organic amine provides corrosion inhibition on the manufacturing line without the requirement of a specific additional corrosion inhibitor. The organic amine will act as a pH buffer for the binder composition until curing of said binder composition.

[0040] Embodiment of the invention will now be described, byway of example only.

[0041] Example 1: Mean dry veil tensile strengths and mean wet tensile strengths of aqueous, curable binder composition Examples of binder compositions (Table 1) tested on non-woven mineral fibre veils are shown in Table 2 with their respective mean dry veil tensile strengths and mean wet tensile strengths. Table 1 Binder composition pKa 1 2 3 4 5 6 DMH (% dry weight) 79.0 79.0 79.0 79.0 79.0 79.0 AmSO4 (% dry weight) 19.7 19.7 19.7 19.7 19.7 19.7 NH3 aq (% dry weight) 9.25 1 TEA (% dry weight) 7.74 1 Morpholine (% dry weight) 8.50 1 DEA (% dry weight) 8.88 1 4-methylmorpholine (% dry weight) 7.38 1 2,4,6-collidine (% dry weight) 7.43 1 Sil 919 (% dry weight) 0.3 0.3 0.3 0.3 0.3 0.3 pH of the binder composition 9.12 8.28 8.73 8.28 7.99 8.04 Key: DMH= dextrose monohydrate (100%, Cargill) (% by dry weight does not take into account the weight of the water of crystallization); AmSO4 = ammonium sulphate anhydrous (Brenntag, 100); NH3 aq = ammonia water (32%, VWR, GPR RECTAPUR); TEA= triethanolamine (97%, BDH Chemicals); DEA= diethanolamine (98%, Sigma Aldrich, Reagent Grade); Morpholine (99.0%, Fluorochem); 4-methylmorpholine (99.0%, Fluorochem); 2,4,6-collidine (99.0%, Fluorochem); Sil 919= Silanil® 919, 3-aminopropyltriethoxysilane(95%, BRB International BV) The % by dry weight of each compound is given by total dry weight of the binder composition The pKa column gives the pKa value of the respective compound from chemistry handbook. Otherwise specified the pKa is measured in water at 25°C. The pH of the binder composition has been measured after all compounds have been mixed according to the protocol specified below. The pH of binder solutions were measured using a 3-point (pH 4.00, 7.00 and 10.01) calibrated Metier Toldeo- SevenEasy pH meter with InLab Expert Pro pH probe. The pH of the binder composition without an organic amine or NH3 aq is of 5.19. The aqueous curable binder compositions of the above Table 1 were prepared by dissolving DMH and AmSO4 in a 1 litre reactor vessel in water at ambient condition (around 20°C) under constant stirring followed by addition of the base compound (NH3 aq or organic amine). Then, Silanil® 919 was then added into the homogeneous binder solution, preceding an initial dilution at 5% w / w in water and stirred to obtain the aqueous, curable binder composition. The binder compositions were prepared at 2.5% total solids weight for veils for tensile strength evaluation. Veil Binder Impreqnation / Curinq: A4-sized glass veils comprising urea formaldehyde (UF) binder were placed into a Carbolite GPC 12 / 36 laboratory chamber furnacefor about 30 minutes at 600 °C to thermally remove the residual UF binder. The resulting UF binder-free glass veils were removed from the oven, allowed to cool to ambient / room temperature over a time period of about 30 minutes, and then fully immersed into a dipping tray (30 cm x 40 cm x 4 cm) comprising about 400 grams of the aqueous, curable binder compositions of Table 1. The binder-impregnated glass veils were then fully cured at 200°C for 8 minutes using a Mathis Labdryer oven (Werner Mathis AG Switzerland). The glass veils were prepared to have 10 wt% of the binder composition being tested (%wt cured binder in the glass veil verified by LOI (loss on ignition)). Dry and Wet Tensile Strength Measurements: The dry tensile strength of the cured, binder-impregnated glass veils was determined using a Testometric M350-10CT mechanical testing instrument loaded with winTest analysis software, version 4.0.10 (Testometric Company Ltd., Rochdale, UK). For each test, a cured, binder impregnated A4 glass veil was cut into eight (8) equal strips having 1) a length of about 100 mm; 2) a width of about 52.5 mm; and 3) a thickness / depth of about 150 pm, and mounted using top- and bottom-mounted tensile grips. Each glass veil strip was tested separately using a 50 kg load cell at an automated test speed of 10 mm / min controlled by winTest analysis software. During the tests, the glass veils strips were placed vertically in the grippers of the mechanical testing instrument and the force and extension were fared to zero during the mounting of the sample to the instrument prior to testing. The winTest analysis software indicated maximum load at peak, stress at peak and modulus (stiffness), and the data presented herein is representative of the mean average of the twenty-four sample strips from three cured A4 veils. The average maximum load at peak was determined and assigned as the tensile strength for each glass veil / binder system. For wet tensile strength analyses, the glass veils were immersed in a Grant Scientific SUB Aqua Plus water bath (Grant Instruments, Cambridgeshire, UK) maintained at a temperature of about 80 °C for about 10 minutes, removed from the water bath and excess water was removed using tissue paper prior to introducing the semi-wet veils, which lacked adsorbed moisture due to dabbing with tissue paper as previously described, to the mechanical testing instrument. Table 2 Binder composition Mean peak dry tensile strength (N) Mean peak wet tensile strength (N) 1 (comparative) 67 49 2 72 44 3 64 45 1 (comparative) 61 27 4 62 27 1 (comparative) 76 59 5 82 41 6 73 40 The results show that the binder compositions with TEA, DEA and morpholine provided equivalent bond strengths compared to binder composition comprising ammonia water while binder compositions with 4-methylmorpholine and 2,4,6-collidine provided reduced wet tensile strengths.

[0042] Example 2: Absorbance Cure Rate The cure rate of the binder compositions 1, 2, 3 and 4 defined in Table 1 were measured using a colorimetric test based on the absorbance of binder extract measured at 470 nm. As the binder cures, it becomes less soluble in water and therefore the concentration of binder is lower resulting in a reduce absorbance measured at 470 nm. In this test, 22.5% made solid binders were made up according to the binders compositions defined above. A 50 pl aliquot of each binder was pipetted onto a strip of Whatman Glass microfibre filter (GF / A Grade) and then cured in a Carboloite PF60 laboratory oven set to 140°C for different times of 1 minute intervals ranging from 2 to 8 minutes. The individual cured spots on the glass filter strip were then placed in 50 ml of distilled water and subject to sonication for 15 minutes to collect binder extract. The collected binder extracts were then measured using a Spectronic Camspec M501 UV-Vis single beam scanning Spectrophotometer. The binder is deemed as cured, when the measured absorbance reaches a plateau. The resulting cure rates can be taken from Figure 1 and Figure 2 from which it is apparent that the binder compositions with TEA, DEA and morpholine provided equivalent cure rate compared to binder composition comprising ammonia water.

[0043] Example 3: Emission Measurements for Oraanoamines Emission measurements for organoamines was tested on binder composition 2 as defined in Table 1 with the protocol defined below. The binder composition was prepared at 37.5% total solids weight. After preparation, 3 ml of the binder composition was transferred to an aluminum dish The binder was then heated at 200°C for 10 minutes on the top shelf of a Genlab MINO / 30 / F / TDIG oven directly under the exhaust outlet, with a distance of 13 cm from the sample pan to the exhaust outlet. The emissions at the exhaust outlet were measured using an organic nitrogen Drager tube with a total of 68 pumps (60 more than required according to the instructions). No organic nitrogen compounds were detected. If organic nitrogen compounds were detected in the emissions a red ring on the yellow background would be observed in the Drager tube.

[0044] Example 4: % Water Pick-Up Screening Test The water prick-up was tested on the binder compositions 1,2, 3 and 4 defined in Table 1 with the protocol defined below, and the results are reported in Table 3 below. 70 mm GF / A grade glass filter discs were dipped in 22.5% made solids binder made according to previously described recipes with the addition of 3% amino-functional silicone (60%, BRB HJS). The dipped sample was then hung on a steel frame with a folded out paper clip and cured in a 200°C Carbolite PF60 laboratory oven for 15 minutes. Cured discs were then weighed and submerged in 200 ml of distilled water for 1 hour. After 1 hour, the samples were removed, dried using a paper towel and then weighed again. The % water absorbed by the cured discs, referred to as water pick-up, was calculated using the following equation: n / t>i7 n* ? rr (Wet Weight-Dry WeightX -% Water PtckUp = -----------— x 100 r \ Dry Weight / Table 3 Binder composition Water pick up (%) 1 (comparative) 87 2 97 3 90 4 84

[0045] Example 5: Ammonia emission in plant Binder composition 2 as defined in Table 1 was used to manufacture glass wool insulation product in plant during one month with the same parameters used to produce glass mineral wool insulation 5 product manufactured with binder composition 1 as defined in Table 1. The ammonia emissions in the stack were measured online and it was found that a reduction of 19% of ammonia emissions was obtained when using the binder composition 2. No significant levels of concern were found for triethanolamine emissions in the stack. 10

Claims

1 A method of manufacturing a mineral fibre productwherein the mineral fibre product is selected from a non-woven mineral fibre veil, mineral wool insulation, glass wool insulation and stone wool insulation, and wherein the method comprises:- applying an aqueous, curable binder composition to non or loosely assembled mineral fibres to provide resinated mineral fibres; and- subjecting the resinated mineral fibres to heat to cure the aqueous, curable binder composition and to form the mineral fibre product;- wherein the aqueous, curable binder composition applied to the mineral fibres comprises:1) reducing sugar(s),2) inorganic ammonium salt(s), wherein the inorganic ammonium salt consists of ammonium sulfate (NH4)2SO4,3) organic amine(s) having a pKa of 7.5 or more and of 9.0 or less, wherein the organic amine(s) is selected from the group consisting of triethanolamine, diethanolamine, morpholine and combinations thereof; and4) optional additive(s), notably silane coupling agent(s)and wherein when (a) represents the total dry weight of the reducing sugar(s), (b) represents the total dry weight of the inorganic ammonium salt(s), and (c) represents the total dry weight of the organic amine(s),(a) + (b) + (c) is at least 90 wt% of the total dry weight of the aqueous, curable binder composition(a) is 60 to 90 wt % of the total dry weight of (a), (b) and (c);(b) is 2.5 to 25 wt % of the total dry weight of (a), (b) and (c); and(c) is 0.2 to 2 wt % of the total dry weight of (a), (b) and (c).

2. The method according to claim 1, wherein the reducing sugar(s) is selected from the group consisting of xylose, dextrose, fructose and combinations thereof.

3. The method according to any preceding claim, wherein the organic amine consists of triethanolamine.

4. The method according to claim 1 or claim 2, wherein the organic amineconsists of diethanolamine.

5. The method according to claim 1 or claim 2, wherein the organic amine consists of morpholine.

6. The method according to any preceding claim, wherein the aqueous, curable binder compositionis a no added formaldehyde binder composition.

7. The method according to any preceding claim, wherein the aqueous, curable binder compositionconsists essentially of, or consists of 1) the reducing sugar(s), 2) the inorganic ammonium salt(s), 3) the organic amine(s) and 4) the optional additive(s).

8. The method according to any preceding claim, wherein the aqueous, curable binder composition comprises 4) the optional additive(s) and wherein the 4) optional additive(s) comprise one or more additive(s) selected from the group consisting of silane coupling agent(s), silicones, dedusting oils and combinations thereof.

9. The method according to any preceding claim wherein the aqueous, curable binder composition comprises 4) the optional additive(s) and wherein when (d) represents the total dry weight of the optional additive(s), (d) is less than 10 wt%, less than 8 wt%, preferably less than 5 wt%, more preferably less than 3 wt%, of the total dry weight of the aqueous curable binder composition.

10. The method according to any preceding claim wherein (a) + (b) + (c) is at least 92 wt%, preferably at least 95 wt%, more preferably at least 97 wt%, even more preferably at least 98 wt%, of the total dry weight of the aqueous, curable binder composition.

11. The method according to any preceding claim wherein (a) is 65 to 90 wt %, preferably 75 to 85 wt %, of the total dry weight of (a), (b) and (c).

12. The method according to any preceding claim wherein (b) is 5 to 25 wt%, preferably 5 to 20 wt %, of the total dry weight of (a), (b) and (c).

13. The method according to any preceding claim wherein (c) is 0.5 to 2 wt%, preferably 0.5 to 1.0 wt%, of the total dry weight of (a), (b) and (c).

14. The method according to any preceding claim wherein the mineral fibre product is a mineral wool insulation product, preferably a mineral wool insulation product which has a thermal conductivity A in the range 0.02 W / mK to 0.05 W / mK when measured at 10°C according to EN12667.

15. The method according to any preceding claim wherein the mineral fibre product is a mineral wool insulation product, preferably a glass wool insulation product, and has a density in the range of 6 to 125 kg / m3, preferably in the range of 8 to 60 kg / m3.

16. The method according to any preceding claim wherein the dry weight of the aqueous binder composition when applied to the non or loosely assembled mineral fibres makes up between 5 to 20 wt% of the total weight of the aqueous binder composition.

17. Use of organic amine(s) having a pka of 7.5 or more and of 9.0 or less in an aqueous, curable binder composition for manufacturing a mineral fibre product, notably in a method according to any preceding claim, to reduce ammonia emissions in plant from the aqueous, curable binder5 composition, wherein the organic amine(s) is selected from the group consisting oftriethanolamine, diethanolamine, morpholine and combinations thereof.

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