Mineral fibre binder based on proteins, saccharides and a crosslinker, a method for making mineral fibre products and uses thereof

Abstract

The invention is directed to aqueous binder composition for MMVF fibres comprising one or more protein(s) of non-plant origin; one or more saccharides and a crosslinker comprising at least two azetidinium functional groups which when cured is biodegradable. Methods for producing MMVF fibres, MMVF fibre products and uses are also disclosed.

Description

[0001] Mineral fibre binder based on proteins, saccharides and a crosslinker, a method for making mineral fibre products and uses thereof

[0002] Description

[0003] Field of the Invention

[0004] The present invention relates to an aqueous mineral fiber binder composition comprising one or more proteins, one or more saccharides and a crosslinker; a method of producing a bonded mineral fibre product; a mineral fibre product comprising mineral fibres bound by a binder and uses thereof.

[0005] Background of the Invention

[0006] Mineral wool products generally comprise man-made vitreous fibres (MMVF) such as, e.g., glass fibre, ceramic fibres, basalt fibres, slag wool, mineral wool and stone wool (rock wool), which are bonded together by a cured thermoset polymeric binder material.

[0007] Mineral fibre mats, or other mineral fibre products are generally produced by converting a melt made of suitable raw materials to fibres in a conventional manner, for instance by internal centrifugation (spinning cup process) or by external centrifuging (cascade rotor process). The fibres are blown into a forming or spinning chamber and, while airborne and still hot, are sprayed with a binder solution and randomly deposited as a mat or web onto a travelling conveyor. The fibre mat is then transferred to a curing oven, e.g. after forming the product into a desired shape, where heated air is blown through the mat or product to cure the binder and (rigidly) bond the mineral fibres together. Phenolic binders, in particular phenol-formaldehyde resole resins are frequently used in the manufacture of mineral fibre insulation materials, such as insulative batts for walls, roof boards, ceiling tiles, insulative coverings for pipes, and the like. Phenol-formaldehyde resins can be economically produced and can be extended with urea prior to use as a binder.

[0008] Various techniques have been used to reduce the formaldehyde emission from formaldehyde-based resins. In particular, various formaldehyde scavengers have been used for that purpose. For instance, urea acts as a formaldehyde scavenger both at, and subsequent to, the manufacture of bonded mineral fibre products. Urea is typically added directly to the phenol-formaldehyde resin to produce a urea-modified phenol-formaldehyde resole resin also called phenol-urea- formaldehyde resole resin. To obtain a typical urea-modified resole binder resin, a mixture of phenol and formaldehyde is reacted with a suitable catalyst in one or more steps. The reaction conditions, temperature, amount of catalyst, etc. are adjusted to favour phenol methylation reaction over condensation reactions. Urea is then added before or after inactivating the resin just prior to use of the resin. Such a resin is typically referred to as a PUF resin, or PUF binder.

[0009] As an alternative to adding formaldehyde scavengers various types of binders have been proposed which are produced without use of formaldehyde. The resulting products thereby exhibit low levels of formaldehyde release and / or result in low risk of emissions of formaldehyde from the production facility.

[0010] Additionally, the existing and proposed legislation directed to the lowering or elimination of formaldehyde emissions have led to the development of formaldehyde-free binders such as, for instance, the binder compositions based on polycarboxy polymers and polyols or polyamines, such as disclosed in EP-A- 583086, EP-A-990727, EP-A-1741726, US-A-5, 318,990 and US-A-

[0011] 2007 / 0173588. Another group of non-phenol-formaldehyde binders are the additionZ-elimination reaction products of aliphatic and / or aromatic anhydrides with alkanolamines, e.g., as disclosed in WO 99 / 36368, WO 01 / 05725, WO 01 / 96460, WO 02 / 06178, WO 2004 / 007615 and WO 2006 / 061249. These binder compositions are water soluble and exhibit excellent binding properties in terms of curing speed and curing density.

[0012] All the above-mentioned binders are not biodegradable after being cured.

[0013] Since some of the starting materials used in the production of these binders are rather expensive chemicals, there is an ongoing need to provide formaldehyde- free binders, which are economically produced.

[0014] A further effect in connection with previously known aqueous binder compositions for mineral fibres is that at least the majority of the starting materials used for the productions of these binders stem from fossil fuels. There is an ongoing trend of consumers to prefer products that are fully or at least partly produced from renewable materials and there is therefore a need to provide binders for MMVF fibres, which are at least partly produced from renewable materials.

[0015] A further effect in connection with previously known aqueous binder compositions for mineral fibres is that they involve components, which are corrosive and / or harmful. This requires protective measures for the machinery involved in the production of MMVF products to prevent corrosion and also requires safety measures for the persons handling this machinery. This leads to increased costs and health issues and there is therefore a need to provide binder compositions for mineral fibres with a reduced content of corrosive and / or harmful materials.

[0016] Accordingly, there is still a need to provide a method for preparing MMVF products, which employs an aqueous binder composition prepared to a large part from renewable materials which are not corrosive or harmful and in the process of which only a small amount of harmful gases is produced and at the same time the MMVF product resulting from the curing has good mechanical properties.

[0017] US2011 / 003522 A describes a soy protein-based binder and a glass wool product comprising the binder. The fibres are formed in a spinning chamber by one or more rotating spinning cups where the molten glass is fiberized. The hot glass wool fibres are then sprayed with the soy protein-based binder using an annular spray ring. Water may be sprayed on the fibres in the spinning chamber prior to addition of the binder in order to cool the newly spun fibres.

[0018] MMVF fibre binders based on hydrocolloids, e.g. animal-based proteins and a crosslinker containing one or more phenol compound(s), e.g. tannins, are described e.g. in WO2017 / 194722 A or in WO2022 / 175310 A.

[0019] Used MMVF fibre products can be recycled and form part of the raw material used to make new MMVF fibre products. This requires collection of MMVF fibre products and logistics to collect and transport the recycled MMVF fibre products from the collection sites to the factories where MMVF fibre products are produced.

[0020] In some rural areas, the transportation distances of used MMVF fibre products to a collection site and / or from a collection site to a MMVF fibre production factory is too long to make recycling economically feasible. Thus, instead, the used MMVF fibre products can end up in landfills.

[0021] For the purpose of the present application, the term "formaldehyde free" is defined to characterize a mineral wool or mineral fibre product where the emission is below 5 pg / m2 / h of formaldehyde from the mineral wool / fibre product, preferably below 3 pg / m2 / h. Preferably, the test is carried out in accordance with ISO 16000 -1 :2004 for testing aldehyde emissions. For the purpose of the present application, the term emissions including factory emissions and / or process emissions, are defined as emission of gaseous and / or air-borne emissions that are a result of the production of mineral fibre products, and which are released into the surroundings form a production facility, e.g. via chimneys.

[0022] For the purpose of the present application, the term Bloom is defined to characterize the strength of a gel and is a test to measure the strength of a gel, such as gelatine. The test determines the weight in grams needed by a specified plunger (normally with a diameter of 0.5 inch / 1.27 cm) to depress the surface of the gel by 4 mm without breaking it. The number of grams is called the Bloom value. The higher a Bloom value, the higher the melting and gelling points of a gel, and the shorter its gelling times. This method is most often used on soft gels. To perform the Bloom test on a soft gel, such as gelatine, an aqueous 6.67wt-% or 12.5 wt-% gelatine solution is kept for 17-18 hours at 10°C prior to being tested. In the present patent application, the Bloom value is measured using a 12.5 wt-% solution unless otherwise specified.

[0023] For the purpose of the present application, the term "biodegradable" is used to characterize a MMVF binder which - after curing - can be at least partly decomposed under aerobic composting conditions, e.g. while using an inoculum either of compost or soil.

[0024] During aerobic composting conditions, organic materials are decomposed mainly into CO2and water by biological activity in the compost, including microbial activity. So, in order for a resin or polymeric material to be biodegradable it has to possess the ability to be partly or fully decomposed by the microbial and / or other biological activity present in compost or a compost inoculum.

[0025] Several certification schemes exist for different products containing plastics to certify towards the end user(s) that the plastics in the product is safe to put into a composting facility, pit or pile, because it is considered biodegradable. In order to get a certification it is required that a plastic material used in a product is tested to be able to decompose at least 90% (absolute, i.e. by weight of the plastic material, or relative to a reference) within a period of up to 180 days when composted under aerobic conditions and a controlled temperature scheme, e.g. at 58°C. A certificate can e.g. be obtained if the plastic component in the product passes the above mentioned target when tested according to certain standards, e.g. ISO 14855-1 (2012) using “Determination of the ultimate aerobic biodegradability of plastic materials under controlled composting conditions - Method by analysis of evolved carbon dioxide (2012)”. When tested according to ISO 14855-1 (2012), the percentage of biodegradation can be given by the ratio of the carbon dioxide produced from the test material to the maximum theoretical amount of carbon dioxide that can be produced from the test material. The maximum theoretical amount of carbon dioxide produced is calculated from the measured total organic carbon (TOC) content.

[0026] The test according to ISO 14855-1 (2012) is typically run for at least 45 days and may run up to 180 days.

[0027] For the purpose of the of the present application, the term "at least partly biodegradable" is used to characterize a MMVF binder which - after curing - can be decomposed at least 20% (absolute, i.e. by weight, relative to the weight of the starting material) within a period of 45 days when composted under aerobic conditions at 58°C according to ISO 14855-1 (2012) (standard test variant, i.e. without vermiculite bed). A fully biodegradable MMVF binder will be 100% converted from the polymeric structure to small molecular degradation products, e.g. carbon dioxide (CO2), water, nitrogen oxides (NOx) or nitrogen gas (N2) etc.

[0028] Indicative tests exist, which can have a shorter duration, and thus allow a faster indication of whether or not a specific product, plastic, resin or binder is biodegradable or not under aerobic composting conditions. In addition, the indicative tests can indicate if a biodegradable product, plastic, resin or binder biodegrades quickly or more slowly and thus requires longer composting time to obtain a tolerable and / or wanted degree of decomposition. The test used in example 11 further below run at 25°C is an example of such an indicative test.

[0029] Accordingly, there is still a need to provide alternative binders for man-made vitreous fibres (MMVF), which exhibits low levels of emissions, in particular emissions originating from production of products made of man-made vitreous fibres (MMVF) and / or low levels of emissions from finished products.

[0030] Additionally, there is also still a need to provide alternative binders for man-made vitreous fibres (MMVF), which are biodegradable or at least partly biodegradable after curing.

[0031] Summary of the Invention

[0032] Accordingly, it is an object to provide an aqueous binder composition suitable for bonding mineral fibres, which overcomes or alleviates the drawbacks of the prior art discussed above.

[0033] Specifically, it is an object to provide an aqueous mineral fibre binder composition, which is environmentally friendly, in particular which is mainly based on renewable source materials, which results in low levels of emission of harmful or unwanted substances, and at the same time having good mechanical properties.

[0034] More specifically, it is an object to provide an aqueous MMVF fibre binder composition, which is biodegradable after curing or at least partly biodegradable after curing. More specifically, it is an object to provide an aqueous MMVF fibre binder composition, in which the speed and / or degree of biodegradation of the cured binder can be tuned according to use or needs without compromising mechanical strength of the MMVF fibre product.

[0035] It is also an object to provide an aqueous MMVF fibre binder composition, in which the speed and / or degree of biodegradation of the cured binder can be balanced relative to the mechanical strength requirements of the cured final product(s).

[0036] It is also an object to provide a MMVF fibre product bound by the cured binder composition.

[0037] These objects are solved by a mineral fibre binder composition in the form of an aqueous binder composition comprising a) one or more protein(s) of non-plant origin; b) one or more saccharide(s) selected from monosaccharides, disaccharides, or oligosaccharides, or combinations or mixtures of two or more thereof, and c) a crosslinker comprising two or more azetidinium functional groups, and wherein the weight ratio of protein(s) to saccharide(s) (P:S) solids is between 75.5: 24.5 and 99:1.

[0038] Furthermore, the degree of biodegradation or decomposition caused by biological activity can be tailored to be high or low by adjusting the ratio of protein(s) to saccharide(s) (P:S) without compromising the mechanical properties of the MMVF product comprising the cured binder.

[0039] Thus, if the binder composition contains ratios of protein in the high end of the P:S ratio range and thus correspondingly low ratio of saccharide(s), the cured binder composition is highly biodegradable and may meet the requirements specified in ISO 14855-1 (2012) and be able to obtain one or more certificates on the binder being biodegradable and / or compostable.

[0040] If the binder composition contains a ratio of saccharides (s) which is increased to a higher level within of the P:S ratio range and thus correspondingly a lower ratio of protein(s), the cured binder composition is still biodegradable, but the biodegradation may occur at a slower rate and / or the maximum level of decomposition may be lower than a binder with a protein ratio in the end of the ratio range.

[0041] Additionally, the majority of the ingredients in the MMVF binder composition are biobased, since at least components a) and b) are based on natural materials and / or materials of natural origin. Thus, the majority of the ingredients in the binder composition are also made from renewable sources since at least components a) and b) are based on compounds which can be derived from plants or animals which naturally occur in the nature.

[0042] When the cured binder used in the man-made vitreous fibres (MMVF) product is biodegradable, the binder can easily be removed from the MMVF fibres by subjecting the product(s) to a composting step. Thus, the MMVF product can easily and safely be disposed of after end of use, e.g. in a composting facility. The man-made vitreous fibres can be left in the compost. Since man-made vitreous fibres (MMVF) originates from melting of inorganic minerals found in nature, e.g. rocks or sand, the inclusion of MMVF fibres from a composted MMVF fibre containing product in a compost mixture is possible without introducing health or environmental hazards. Also, the mineral wool fibres in the compost can provide structure in the compost and can act as a soil improver, e.g. enhancing a looser and / or porous soil structure.

[0043] When the binder in the MMVF fibre product is biodegradable, the binder can also biodegrade over time, simply by leaving the product(s) in outdoor conditions for a period of time. Thus, even if disposed under outdoor conditions, e.g. at a landfill, the binder will decompose over time and the MMVF fibre products will over time disintegrate whereby the MMVF fibres will be mixed into soil or earth etc. Thus, the MMVF fibre products will safely and easily disintegrate after end of use.

[0044] Therefore, the present disclosure is also directed to a method for disposing of a mineral fibre product comprising mineral fibres bound by a biodegradable binder resulting from the curing of an aqueous binder composition according to the present disclosure, and comprising the steps of

[0045] - optionally disintegrating the mineral fibre product, followed by

[0046] - subjecting the mineral fibre product to a composting step in which the biodegradable binder is at least partly decomposed by biological activity.

[0047] The present binder composition is surprisingly at least at least partly biodegradable after being cured. Said cured MMVF binder can thus be decomposed at least 20% within a period of 45 days when subjected to composting conditions at 58°C according to ISO 14855-1 (2012) (standard test variant using an inoculum from compost, i.e. without vermiculite bed).

[0048] Preferably, the composting step is performed under aerobic conditions.

[0049] During aerobic composting conditions, the cured binder or at least part thereof will decompose into CO2 and water by biological activity in the compost, including microbial activity. This allow for disposing of the MMVF products by composting, e.g. in an industrial composting facility, where the binder will be degraded by (micro)biological activity and the MMVF fibres is blended with the compost leaving the compost facility.

[0050] The mineral fibre product can be introduced into the composting step as is. Alternatively, the mineral fibre product can be disintegrated, e.g. chopped or grinded into smaller particulates e.g. having a diameter of somewhere between 1 - 100 mm. The disintegrating can speed up the biodegradation of the binder in the mineral fibre product. Further, the reduced particulate sizes can result in that the mineral fibres after completion of the composting step can remain in the compost and can provide structure in the compost. Thus, the mineral fibres can act as a soil improver, e.g. by enhancing a looser and / or porous soil structure in the compost or the soil that is mixed with the compost.

[0051] The present disclosure also relates to the use of an aqueous binder composition according to the present disclosure for production of a mineral fibre products where binder is at least partly biodegradable after curing and thus can be decomposed at least 20% (by weight of the starting material) within a period of 45 days when composted under aerobic conditions at 58°C according to ISO 14855- 1 (2012).

[0052] The aqueous binder according to the present disclosure is based on a mixture of one or more saccharides and one or more proteins which - after curing - are crosslinked with the azetidinium functional crosslinker as outlined above.

[0053] The unique crosslinking reactivity of the azetidinium functional crosslinker towards both proteins and saccharides is central to the present binder technology. In brief, and without being bound by theory, the electrophilic four membered azetidinium rings (see formula I further below) in the crosslinker can both self-crosslink and co-crosslink with the saccharides as well as with the proteins to generate covalent bonds. This occurs by nucleophilic attack on the a-position of the azetidinium ring of a nucleophile from the saccharide or protein leading to ring opening and formation of a covalent bond.

[0054] The mineral fibre aqueous binder composition of the present disclosure (may in the following be abbreviated to “the binder”) is defined to encompass an aqueous binder composition which is to be used for binding mineral fibres together to form a coherent product. The binder comprises no toxic components and is thus not only formaldehyde free, but also ammonia free. The emissions resulting from production and / or curing of the present aqueous binder composition are among the lowest of any of the currently available mineral fibre binders which also exhibits low formaldehyde emissions from the products made thereof.

[0055] Furthermore, the low level of emissions resulting from application of the binder can be handled in conventional abatement systems and thus reduces or even eliminates the need for installing new abatement equipment, such as, for example catalyst(s) to reduce or eliminate emissions of volatile organic compounds (VOC), e.g. formaldehyde; and / or nitrogen containing compounds, for example ammonia and / or nitrogen oxides (NOx).

[0056] The present mineral fibre binder according to the present disclosure also provides mineral fibre products, such as thermal or acoustic insulation products which exhibit the following advantages over the prior art:

[0057] - surprisingly, good mechanical strength properties in mineral fibre products bound by the binder which are the result of balance between protein and saccharide content when crosslinked with the azetidinium functional crosslinker

[0058] - the aqueous mineral fibre binder composition is biodegradable or at least partly biodegradable after curing, without compromising strength properties of the MMVF fibre products

[0059] - the used products can be disposed of by composting, e.g. in an industrial composting step,

[0060] - the speed and / or degree of biodegradation of the cured binder can be tuned according to use or needs without compromising strength properties of the MMVF fibre products

[0061] - minimizing emissions of potential hazardous substances from production facilities - provides MMVF fibre products, e.g. for thermal or acoustic insulation, which can be classified as formaldehyde free, when tested in accordance with ISO 16000 - 1 :2004

[0062] - reduces the degree of pre-drying of the mineral fibre binder composition, which can be seen when using some binders with high contents of proteins, e.g. gelatines.

[0063] - minimizing the content of crosslinker while optimizing the mechanical strength in mineral fibre products, which can be obtained by using the azetidinium functional crosslinker

[0064] - low risk of corrosion in production equipment in contact with the aqueous binder composition. The binder composition does not contain any acidic components, and the binder composition is kept at neutral - or near neutral pH, which also contributes to reducing the risk of corrosion on production equipment.

[0065] In addition, the present mineral fibre binder according to the present disclosure thus provides a low carbon footprint; and / or is a sustainable and environmentally friendly alternative to conventional petrochemical ly based binders, such as phenol-formaldehyde based binders, e.g. because

[0066] - the majority of the ingredients are of non-petrochemical origin

[0067] - the majority of the ingredients are from renewable sources; in particular the protein source(s) and the saccharide source(s) are of natural origin, such as originating from animals and / or plants or of microbial origin or a product made of recombinant organisms, and are thus from renewable sources

[0068] - extremely low emissions from production facilities when compared to traditional mineral fibre binder(s)

[0069] The environmental benefits can thus be met without compromising other properties of the mineral fibre products, which are made with the binder composition according to the present disclosure, e.g. in thermal and / or acoustic insulation products. Thus, the environmental benefits of low levels of binder related emissions can be met without compromising strength requirements (e.g. unaged strength, aged strength, compression strength, delamination strength and / or point load) that are required, e.g. from thermal and / or acoustic insulation products.

[0070] The mineral fibre binder composition according to this disclosure exhibit excellent unaged and aged mechanical strengths at levels that are comparable or higher than conventional phenol-formaldehyde based binders.

[0071] Thus, products made with mineral fibre binders described herein exhibit excellent strength properties, which are at comparable with commonly known and widely used mineral fibre binders based on phenolic — formaldehyde resins.

[0072] Unaged mechanical strength and aged mechanical strength is determined using the three-point bending test described in the experimental section. This laboratory test made on bars comprising mineral fibre shots isolated from mineral wool fabrication and the binder composition as explained in the experimental section.

[0073] To provide satisfactory mechanical strengths (unaged, aged (in water bath or autoclave) the obtained values should preferably be at level with the corresponding values of PUF (reference binder A)

[0074] Compositions without saccharides display unsatisfactorily low strength (unaged and autoclave aged) (see fig. 1 ). Compositions without protein, on the other hand, also exhibit unsatisfactorily low strength (unaged and autoclave aged, see fig. 1 ) and / or require high concentration levels of the azetidinium functional crosslinker to achieve satisfactory unaged and aged mechanical strengths. This illustrates the necessity for including both proteins and saccharides, and possibly also the the azetidinium functional crosslinker, in the binder composition. The improvements described for the mixed mineral fibre binder composition are to such an extent that they generally cannot be explained by additive effects but clearly shows a synergistic interaction in the resulting binder composition from the protein components and from the saccharide components when crosslinked with the azetidinium functional crosslinker (see fig. 1 ).

[0075] Thus, the binder composition preferably exhibits a weight ratio of protein to saccharide between 99:1 and 80:20 or such as between 95:5 and 80:20 more preferred between 90:10 and 80:20.

[0076] Alternatively, the binder composition may exhibit a weight ratio of protein to saccharide (P:S) in the range of 80:20-75.5:24.5, or 90:10-75.5:24.5 or 95:5- 75.5:24.5.

[0077] The protein content in the binder composition is preferably in the range of 69.5- 91 .4% by weight of binder component solids, or preferably 73.8-91 .4% by weight of binder component solids, such as 73.8-87.7 % by weight of binder component solids or more preferred 73.8-83.1 % by weight of binder component solids.

[0078] The saccharide content in the binder is preferably in the range 0.9-22.6% by weight of binder component solids, such as 0.9-18.5 % by weight of binder component solids, or preferably 4.6-18.5 % by weight of binder component solids or more preferred 9.23-18.5% by weight of binder component solids.

[0079] Unless otherwise stated, it should be clear the indication of proteins, saccharides and crosslinker throughout the description, e.g. with respect to the weight ratio of protein to saccharide (P:S), the protein content, the saccharide content or the crosslinker content, relates to these components of the inventive binder as defined, i.e. to a) the one or more protein(s) of non-plant origin; b) the one or more saccharide(s) selected from monosaccharides, disaccharides, or oligosaccharides, or combinations or mixtures of two or more thereof, and c) the crosslinker comprising two or more azetidinium functional groups, respectively.

[0080] The optimum in terms of mechanical strengths is thus a balance between protein to saccharide ratios and the amount of azetidinium crosslinker used in the aqueous binder.

[0081] The reaction losses generally increase with increasing saccharide content. The optimum in terms of atom economy is thus towards high protein content.

[0082] The curing onsets and endsets generally increase with increasing saccharide content. Conversely, the degree of pre-drying generally decreases with increasing saccharide content. The optimum in terms of curing properties is thus a compromise between the two factors, with the pre-drying degree arguably being the most important.

[0083] Thus, the present binder composition preferably has either

[0084] A: wherein the protein content in the binder composition is 69.5-91 .4% by weight of binder component solids and the saccharide content in the binder composition is in the range of 0.9-22.6% by weight of binder component solids and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1 .5-18% by weight of binder component solids or preferably 2-16% by weight of binder component solids or preferably 5-15% by weight of binder component solids; or

[0085] B: wherein the protein content in the binder composition is 73.8-91 .4% by weight of binder component solids, and saccharide content in the binder composition is in the range of 0.9-18.5% by weight of binder component solids and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18% by weight of binder component solids or preferably 2-16% by weight of binder component solids or preferably 5-15% by weight of binder component solids; or C: wherein the protein content in the binder composition is 73.8-87.7% by weight of binder component solids and the saccharide content in the binder composition is in the range of 4.6-18.5% by weight of binder component solids and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18 % by weight of binder component solids or preferably 5- 15% by weight of binder component solids or preferably 2-9% by weight of binder component solids; or

[0086] D: wherein the protein content in the binder composition is 73.8-83.1 % by weight of binder component solids and the saccharide content in the binder composition is in the range of 9.2-18.5 % by weight of binder component solids, and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1 .5-18 % by weight of binder component solids or preferably 2-16 % by weight of binder component solids or preferably 5-15% by weight of binder component solids.

[0087] It appears that changing pH of the aqueous mineral fibre binder composition does not seem to significantly affect the mechanical properties the MMVF products made with the binder. It appears, e.g. from fig. 6, that the unaged strength and autoclave aged strength displays a (small) optimum obtained at around pH 8. Thus, the aqueous binder may have pH in the range of 4.5 to 9.5, such as 6.0 to 9.0. In order to reduce risk of corrosion or similar issues in the production equipment and / or reduce risk hazards to production staff which may come into contact with the aqueous binder composition, it is preferred that the aqueous binder composition has neutral pH or near neutral pH, such as pH of 6.5-8.0.

[0088] The present disclosure also relates to a method of producing mineral fibres bound by a mineral fibre binder as described above and below. This method is described in further details below.

[0089] The aqueous mineral fibre binder composition is simply prepared by adding the binder components to water. The binder components can simply be mixed with water to form the final binder composition prior to application to the mineral fibres. Typically, protein(s) and saccharide(s) are added as solids, concentrates, syrups and / or aqueous solutions to the water. The preparation of the mineral fibre binder composition can be performed by conventional means e.g. in a mixing tank or by inline mixing.

[0090] The binder components can be mixed into water in any order.

[0091] Preferably, the azetidinium functional crosslinker is added as the last component, such as shortly or immediately before introducing the binder into the mineral fibres to avoid any unintentional setting, e.g. of gelatins, in the event that the mineral fibre binder composition is allowed to stand in a mixing tank or holding tank for an extended time interval before being added to the mineral fibres.

[0092] The water may have a temperature of 20-70°C, such as 30-60°C when adding the protein(s) and / or saccharide(s) in order to ensure fast and effective dissolution thereof. If the mineral binder composition is held in a tank for an extended period before being used, either with or without the crosslinker added thereto, it may be preferred to maintain the binder composition at a temperature of 20-70°C, such as 30-60°C avoid any unintentional setting.

[0093] If collagen type proteins are used, such as gelatin(s), the elevated temperature of the water and / or binder composition ensures that the collagen type proteins e.g. gelatins, do not gel. Gelled gelatins in production equipment are unwanted as it can cause blocking of equipment, e.g. pipes valves etc., and may result in unwanted production stop(s) while cleaning of the blocked equipment.

[0094] Alternatively, the binder can be prepared as a 2-component binder where one or both component(s) comprises azetidinium functional crosslinker. In this case a first component comprises the one or more protein(s) and the optionally azetidinium functional crosslinker, and a second component comprises the one or more saccharide(s) and optionally the azetidinium functional crosslinker. First and second components are mixed before introducing the resulting binder composition into the mineral fibres, such as shortly or immediately before introducing the binder composition into the mineral fibres. The first and second components are e.g. mixed by mechanical means, such as in a mixer, a stirred mixing tank or by inline mixing.

[0095] If relevant, one or more additives such as hydrophobic agents, such as silicones and / or oils, or hydrophilic agents can be added to the binder composition, e.g. during mixing thereof, or the additive(s) may alternatively be added separately to the binder, e.g. via a separate inline mixing port, prior to mixing the binder with the mineral fibres, such as immediately before adding the binder composition to the mineral fibres. Alternatively, the one or more additive(s) may be added to the mineral fibres via dedicated injections means, such as a second set of injection nozzles.

[0096] The present disclosure also relates to mineral fibre products bound by an aqueous mineral fibre binder composition as described above and below. When cured a coherent product is formed. These products are described in further details below.

[0097] Other uses of the mineral fibre binder and methods in producing mineral fibre products are also described in further detail below.

[0098] Protein component(s) of the binder

[0099] The binder comprises, as component a), one or more protein(s) of non-plant origin.

[0100] For the present disclosure, the term “non-plant protein” encompass proteins from animals, fungi, microorganisms, such as bacteria, and / or non-vascular plants. Animals include vertebrates, or invertebrates. Animals are composed of eukaryotic cells, which are surrounded by an extracellular matrix composed of protein, including collagen type proteins and glycoproteins. Vertebrates include mammals, birds, amphibians, fish and reptiles. Invertebrates include insects, mollusks, crustacean (arthropods), cnidaria (corals, sea anemones, jellyfish, sponges etc.) and worms.

[0101] Non-vascular plants are plants without a vascular system. Non-vascular plants lack lignified water-conducting tissues. Non-vascular plants comprise algae, e.g. green algae, and bryophytes (mosses, hornworts and liverworts).

[0102] Preferably, the protein component of the binder, i.e. component a), comprises one or more protein(s) selected from source(s) comprising

[0103] - collagen or collagen derivatives, such as of animal origin, microbial origin and / or obtainable by use of recombinant technology, such as collagen or collagen derivatives, such as gelatine, such as partly hydrolysed gelatine; such as collagen type proteins of bovine, porcine, marine and / or recombinant sources,

[0104] - animal based proteins other than collagen type proteins, such as proteins from milk (casein, whey); proteins from eggs, such as albumin; proteins from marine animal sources;

[0105] - proteins from jellyfish; proteins from insects, such as silkworms, such as sericin; proteins originating from microorganisms, such as by means of recombinant techniques, such as natural and / or genetically modified proteins from fungi, algae, such as microalgae, or bacteria, in particular yeasts, such as yeast protein, yeast extract and / or undenatured or hydrolyzed or at least partly denatured mycoprotein; or mixtures of two or more thereof.

[0106] Alternatively, the binder may comprise a combination of 2 or more proteins, in particular two or more different collagen type proteins; one or more first protein(s) selected from a collagen type protein and one or more second protein(s) selected from animal-based protein(s) other than collagen type proteins; or two or more different proteins of animal origin. The binder composition preferably comprises at least one protein, which is selected from source(s) comprising collagen or collagen derivatives, such as gelatine, such as partly hydrolysed gelatine, such as collagen or gelatine from bovine, porcine, marine and / or recombinant sources.

[0107] The one or more proteins preferably comprises collagen type proteins or partly hydrolysed collagen type proteins, such as gelatine or partly hydrolysed gelatine, where said protein(s) have an average molecular weight of 1 -100 kDa, such as 1.5 - 50 kDa, or preferably 2-30 kDa or preferably 1 -30 kDa.

[0108] In particular, the term gelatine or hydrolysed gelatine also encompass food grade gelatines, technical grade gelatines, animal glues, bone glues or fish gelatine or fish glues. Food grade is defined as being suitable for inclusion in human or animal food or fodder products, while technical grade is defined as being non-suitable for inclusion in human or animal food or fodder products.

[0109] Marine gelatines or fish glues derived from fish, especially gelatines from fish harvested in cold water seas, may have a different chemical composition and / or structure when compared to collagen type proteins, e.g. gelatines, obtained from mammals or other animal sources. Thus, fish gelatine and / or fish glue may exhibit low Bloom values, e.g. as low as 0, when determined with the below described standard method for determining Bloom values.

[0110] Preferably, the mineral fibres are mixed with an aqueous protein containing binder composition comprising the at least one protein, at least one saccharide and the at least one crosslinker.

[0111] The binder composition preferably has a content of the at least one protein, preferably gelatine, in the range of 69.5-91.4% by weight of binder component solids, or preferably 73.8-91.4% by weight of binder component solids, such as 73.8-87.7% by weight of binder component solids or more preferred 73.8-83.1 % by weight of binder component solids.

[0112] Collagen is a very abundant material in living tissue: It is the main component in connective tissue and constitutes 25-35 percent of the total protein content in mammals. Gelatine is derived from chemical degradation of collagen. Gelatine may also be produced by recombinant techniques. Gelatine is water soluble and has a molecular weight of 10.000 to 500.000 g / mol, such as 30.000 to 300.000 g / mol dependent on the grade of hydrolysis. Gelatine is a widely used food product, and it is therefore generally accepted that this compound is totally nontoxic and therefore no precautions are to be taken when handling gelatine.

[0113] Gelatine is a heterogeneous mixture of single or multi-stranded polypeptides, typically showing helix structures. Specifically, the triple helix of type I collagen extracted from skin and bones, as a source for gelatine, is composed of two alpha 1 (1 ) and one alpha2(l) chains.

[0114] Gelatine solutions may undergo coil-helix transitions.

[0115] A type gelatines are produced by acidic treatment. B type gelatines are produced by basic treatment.

[0116] The gelatine can also be further hydrolysed to smaller fragments of down to 3000 g / mol (3 kDa) or even as low as down to 1000 g / mol (1 kDa).

[0117] On cooling a gelatine solution, collagen like helices may be formed. Gelatine may form helix structures.

[0118] Thus, the cured binder comprising protein may comprise helix structures. Preferably, the at least one protein is a low strength gelatine, such as a gelatine having a gel strength of 20 to 125 Bloom (at 6.67 wt%).

[0119] Alternatively, the at least one protein may be a medium strength gelatine, such as a gelatine having a gel strength of 125 to 180 Bloom (at 6.67 wt%).

[0120] Alternatively, the at least one protein may be high strength gelatine, such as a gelatine having a gel strength of 180 to 300 Bloom (at 6.67 wt%).

[0121] Proteins or gelatines, including technical grade proteins or gelatines, animal glues, bone glues or fish glues, may be used and may exhibit a Bloom (at 12.5 wt%) of 0-250, such as 0-200, or preferably 0-40 or 40-175.

[0122] In a preferred variant, the gelatine is preferably food grade and / or technical grade gelatine originating from one or more sources from the group consisting of mammal, bird species, such as from cow, pig, horse, fowl, and / or from fish, such as from scales, bones or skin of fish or animal glues, bone glues or fish glues.

[0123] The carboxylic acid groups in gelatines may also interact strongly with trivalent and tetravalent ions, for example aluminum salts. This is especially true for type B gelatines, which contain more carboxylic acid groups than type A gelatines.

[0124] The binder composition may comprise at least two proteins, wherein a first protein is selected from collagen or collagen derivatives, preferably gelatine, such as of animal origin, microbial origin and / or obtainable by use of recombinant technology; the second protein is at least one selected from the group consisting of proteins from animal sources different from the first protein, such as protein from milk (casein, whey), eggs; proteins from jellyfish, proteins from insects, such as silk worms, such as sericin, or mussel foot protein, or proteins from proteins produced by microorganisms and / or by recombinant techniques, such as natural and / or genetically modified proteins from fungi, algae, such as microalgae, or bacteria, in particular yeasts, such as yeast protein, yeast extract and / or undenatured or hydrolyzed or at least partly denatured mycoprotein.

[0125] In a variant of the disclosure, the protein containing binder composition does not comprise a protein from vegetable source(s) such as soybeans (soy protein).

[0126] Preferably, the first protein is a collagen type protein as discussed above. The protein may be gelatine and / or partly hydrolysed gelatine, and one or more additional proteins may be another of the non-plant-based proteins as discussed above.

[0127] The at least one protein preferably contains 50 to 400, such as 100 to 300 (hydroxy proline + proline) residues per 1000 amino acid residues.

[0128] The mineral fibre binder composition according to this invention exhibit excellent unaged and aged mechanical strengths at levels that are comparable with conventional phenol-formaldehyde based binders. From the experimental section of this disclosure, it is clear that the present binder composition can exhibit unaged and aged mechanical strengths, which are comparable with or even higher than the corresponding values of conventional phenol-formaldehyde based binders. From the experimental section it also appears that the high values for unaged and aged mechanical strengths can be obtained using a wide range of food grade or technical grade or partially hydrolysed collagen-type proteins from porcine, bovine and / or fish sources, e.g. with average molecular weights below 100 kDa, or 30 kDa or even as low as 1 -3 kDa.

[0129] Pure gelatines with considerably higher molecular weights, such as up to 30-100 kDa may also be used, but more care should be observed when preparing and / or storing the binder made with these gelatines as these gelatines tend to be setting quickly. Premature setting of gelatines can be a reduced or even avoided by mixing and / or storing the binder at elevated temperatures as discussed above.

[0130] Saccharide com

[0131] Component b) in the aqueous binder is in the form of one or more saccharides.

[0132] Thus, the one or more saccharide(s) is selected from

[0133] - monosaccharides, such as dextrose (glucose), xylose, fructose, ribose, arabinose, lyxose, allose, altrose, mannose, gulose, iodose, galactose and / or talose;

[0134] - disaccharides, such as sucrose, lactose, maltose, trehalose and / or cellubiose;

[0135] - oligosaccharides, such as trisaccharides, such as melezitose, raffinose, maltotriose; tetrasaccharides, pentasaccharides or hexasaccharides, such as maltoacis, in particular low molecular mass maltodextrins;

[0136] - glucose syrup and / or combinations or mixtures of two or more thereof.

[0137] The one or more saccharides are preferably one or more reducing saccharides selected from

[0138] - monosaccharides, such as dextrose (glucose), xylose, fructose, ribose, arabinose, lyxose, allose, altrose, mannose, gulose, iodose, galactose and / or talose;

[0139] - disaccharides, such as lactose, maltose, and / or cellobiose;

[0140] - oligosaccharides, such as trisaccharides, such as, maltotriose; tetrasaccharides, pentasaccharides or hexasaccharides, such as maltodextrins, in particular low molecular mass maltodextrins;

[0141] - glucose syrup. Mineral wool products made with binder compositions comprising one or more reducing saccharides exhibit higher unaged and aged strengths when compared to mineral wool products made with binder compositions comprising non-reducing sugars.

[0142] Mixtures of two or more saccharides may comprise two, three, four, five, six or more different saccharides.

[0143] Alternatively, the mixture may comprise an unknown mixture of mono- , di- and / or oligosaccharides, resulting from e.g. enzymatic decomposition of polysaccharides into mono-, di- and / or oligosaccharides.

[0144] Additionally, or alternatively the mixture of saccharides may arise from oxidation and / or hydrolysis of polysaccharides.

[0145] Preferably, the one or more saccharide(s) have a molecular mass of 0.15- 4.0 kDa, such as 0.15 -3.5 kDa, such as 0.15 -1 .5 kDa, such as 0.15 -1 .2 kDa.

[0146] The one or more saccharide(s) may be selected from a saccharide having a dextrose equivalent (DE) of 0 to 100.

[0147] A preferred saccharide is dextrose, or a dextrose source, such as glucose syrup, preferably a glucose syrup having a DE of 15 to 100, in particular of 25 to 100, more particular 30 to 100 or such as 35 to 100.

[0148] Preferably, the one or more saccharide(s) is dextrose or a dextrose source having a DE of 85 to less than 100.

[0149] Preferably, the component (b) is a hexose, such as a glucose, such as dextrose, such as a fructose, a galactose, and / or a mannose, and / or a pentose such as a xylose, an arabinose, rhamnose and / or ribose and / or mixtures thereof. In the present context, monosaccharide is defined as a saccharide or a sugar, indicating that it is a molecule composed of only one saccharide unit. At times monosaccharides are referred to as “simple sugars” or just “sugars”. Monosaccharides are the monomeric units of oligosaccharides and polysaccharides. Polysaccharides contain more than 10 monosaccharide units, whereas oligosaccharides contain 3 to 10 saccharide units joined by glycosidic linkages. Most monosaccharides and oligosaccharides are obtained by hydrolysis of polysaccharides into smaller units by means of heat, acid and / or enzymes. Most common monosaccharides include glucose (dextrose), fructose (levulose), ribose, xylose, galactose and glyceraldehyde.

[0150] All monosaccharides are reducing sugars, i.e. capable of acting as a reducing agent, along with some disaccharides, some oligosaccharides and some polysaccharides. Monosaccharides can be divided into two groups, namely aldoses, which have an aldehyde group, and the ketoses, which have a ketone group. Ketoses must first tautomerize to aldoses before they can act as reducing sugars. In an alkaline solution, a reducing sugar forms some aldehyde or ketone, which allows it to act as a reducing agent. In such a reaction, the sugar becomes a carboxylic acid.

[0151] Examples of disaccharides being reducing sugars are lactose, maltose and cellobiose, which are reducing sugars, whereas disaccharides such as sucrose and trehalose are non-reducing sugars.

[0152] An example of a trisaccharide being a reducing sugar is maltotriose.

[0153] Starch may be used as a raw material for various carbohydrates such as glucose syrups (also known as corn syrups in US) and dextrose. For commercial manufacture of crystalline dextrose, an aqueous slurry of starch is subjected to hydrolysis by means of acid and / or enzyme(s). Depending on the reaction conditions employed in the hydrolysis of starch, a variety of mixtures of glucose and intermediates is obtained which may be characterized by their DE number. DE is an abbreviation for Dextrose Equivalent and is defined as the content of reducing sugars, expressed as the number of grams of anhydrous D-glucose per 100 g of dry matter in the sample, when determined by the method specified in International Standard ISO 5377-1981 (E). This method measures reducing end groups and attaches a DE number of 100 to pure glucose (=dextrose) and a DE of 0 to pure starch. Sucrose actually has a DE of zero even though it is a disaccharide, because the reducing groups of both monosaccharides are connected, so there are no remaining reducing groups.

[0154] Hydrolytic cleavage of the starch may be stopped at different stages of the process resulting in carbohydrate mixtures (sugar syrups) having different DE numbers, i.e. having different molecular weight distribution and different reactivity. The starting point for the process is purified starch milk, i.e. a native starch such as com or cassava potato, which has been treated by e.g. cleaning, milling, washing and made into a slurry preparation.

[0155] Only glucose syrup of high DE can crystallise easily and yield a product in powder or granular form. A most popular crystallised product is dextrose monohydrate with application in medicine and chewing tablets. Dextrose monohydrate is pure glucose (DE 100).

[0156] The number of reducing groups are inversely proportional to the molecular weight of solid products (DE(%)= (Mgiucose / Mn* 100, where Mgiucose is the molecular weight of D-glucose and Mnis the “molecular weight” of the syrup solids).

[0157] Lactose is derivable from the condensation of galactose and glucose. Maltose is produced by hydrolysis of starch using the enzyme [3-amylase. Sucrose is typically obtained by being extracted and refined from either sugarcane or sugar beet, and / or can be prepared synthetically.

[0158] Maltodextrin is an oligosaccharide derived from any starch via hydrolysis with acid and / or enzyme(s). Maltodextrins consist of D-glucose units connected in chains of variable length. Most maltodextrin molecules are maltooligosaccharides, i.e. maltodextrin products are mixtures of maltooligosaccharides, which mixtures have average DE values of between 3 to 20. A lower DE value means the polymer chains are longer (contain more glucose units) whereas a higher DE value means the chains are shorter. Continued hydrolysis of starch with an acid and / or enzymes results in syrups known as glucose syrups (com syrups).

[0159] With lower DE numbers, the syrup gradually loses its tendency to crystallise. Below approximately 45 DE, the syrup can be concentrated into a stable, noncrystallising liquid, for instance, standard 42 DE syrup which finds widespread use in canned fruit preserves, ice cream, bakery products, jam, candy, and all kinds of confectionery.

[0160] The more high-molecular components of the starch hydrolysate (sugar syrup) do not contribute significantly to the formation of the cross-linked binder network. It has been shown that the high-molecular species in the crude hydrolysate do not negatively influence the binder properties in terms of hydrolytic stability and durability.

[0161] Preferably, the molecular mass (kDa) of the saccharides is less than 1 kDa (less than an hexamer - the smallest of the two maltodextrins).

[0162] The saccharide component is preferably selected from mono-, di- and trisaccharides, in particular dextrose, fructose, xylose, ribose, galactose, glyceraldehyde, lactose, maltose, raffinose, and the hydrates, especially monohydrates, thereof, or mixtures of two or more thereof. Such mixtures are preferably maltodextrins or glucose syrups, and more preferably glucose syrups with a dextrose equivalent value of DE = 30 to less than 100, such as DE = 60 to less than 100, such as DE = 60 to 99, such as DE = 85 to 99, such as DE = 95 to 99. The term “dextrose” as used in this application is defined to encompass glucose and the hydrates, especially monohydrates, thereof such as D-glucose.

[0163] The saccharide component is preferably having a DE value of 60 to less than 100, in particular 60 to 99, more particular 85 to 99.

[0164] The saccharide component is preferably a source containing dextrose and having a DE value of 90 to less than 100.

[0165] The saccharide component is alternatively selected from hexoses, in particular allose, altrose, glucose, mannose, gulose, idose, galactose, talose, psicose, fructose, sorbose and / or tagatose; and / or pentoses, in particular arabinose, lyxose, ribose, xylose, ribulose and / or xylulose; and / or tetroses, in particular erythrose, threose, and / or erythrulose.

[0166] The saccharide component is alternatively selected from a hexose, such as a glucose, such as dextrose, a fructose, a galactose, and / or a mannose; and / or a pentose such as a xylose, an arabinose, rhamnose and / or ribose; and / or mixtures thereof.

[0167] The saccharide component is preferably present in the aqueous binder composition is in the range of 0.9-22.6% by weight of binder component solids, such as 0.9-18.5 % by weight of binder component solids, or preferably 4.6-18.5 % by weight of binder component solids or more preferred 9.23-18.5% by weight of binder component solids.

[0168] Since saccharides are comparatively inexpensive compounds and are produced from renewable materials, the inclusion of saccharide component(s) in the aqueous binder allows for an ecological and economic advantageous production of the binder.

[0169] The mineral fibre binders according to the present disclosure preferably exhibits unaged and aged mechanical strengths (other than wet strength) that are comparable or higher than those of the conventional phenol-formaldehyde (PUF) binders. The high levels of unaged and aged strength were generally observed for the use of shorter chain carbohydrates in particular reducing saccharides, in particular mono-, di- and trisaccharides or glucose syrups. Longer carbohydrates with higher average molecular weights starting from 3.6 kDa, which includes maltodextrin also resulted in lower unaged and aged mechanical strengths when compared to binders with dextrose but still comparable or higher than PUF (see fig. 7).

[0170] The dextrose source is e.g. crystalline dextrose, such as dextrose monohydrate or a glucose syrup, such as glucose syrup having a DE of 60 to 100, in particular of 60 to 99, more particular 90 to less than 100 or such as 85 to 99.

[0171] Crosslinking component

[0172] A crosslinker is used to crosslink the protein component(s) and / or carbohydrate components.

[0173] The crosslinker comprises two or more azetidinium functional groups (AZR), see formula I. Azetidinium group (AZR) where X is an anion, such as halogen anion, in particular Cl’ or Br.

[0174] The term azetidinium functional group(s) is defined to encompass azetidinium (i.e without the hydroxy group shown in formula I) as well as substituted azetidinium, preferably hydroxyazetidinium (i.e. with the hydroxy group as shown in formula I).

[0175] The azetidinium functional groups are preferably chemically bonded with a polymer, such as a homopolymer or a copolymer chain, comprising one, two or more non-azetidinium monomer units incorporated into the polymer structure.

[0176] The crosslinker is, preferably, a thermosetting crosslinking polyazetidinium polymer / resin comprising two or more azetidinium functional groups. Said crosslinker is preferably a polyamidoepihalohydrin polymer or a polyaminoamidoepihalohydrin polymer or a polyamidoamineepihalohydrin polymer.

[0177] Such polymers are also known as polyamidoamine-halohydrin or generally polyamide -halohydrin resins.

[0178] Polyamidoamine-halohydrin resins can be formed as reaction products of a polyamine or a polyamidoamine and a halohydrin (e.g., epichlorohydrin or epibromohydrin). Polyamidoamines, in turn, are prepared from the reaction of a polyamine and a polyacid. Suitable polyamines include, but are not limited to, polyalkylene polyamines such as diethylenetriamine or triethylenetetraamine. Mixtures of polyamines are also applicable. Suitable polyacids include diacids such as succinic acid, adipic acid, oxalic acid, phthalic acid, etc. Depending on the mole ratio of the polyamine and polycarboxylic acid, the resulting polyamidoamine may retain predominantly primary amine groups or predominantly carboxylic acid groups at the terminal polymer ends. These termini may also have secondary or tertiary amine moieties.

[0179] The crosslinker is obtainable by reacting polyamidoamine resin with a halohydrin, preferably epichlorohydrin or epibromohydrin, and / or wherein the polyamidoamine resin is obtainable by reacting a polyamine and a polycarboxylic acid, and / or wherein the polyazetidinium polymer is the reaction product of epichlorohydrin or epibromohydrin (or a mixture thereof), and a polyamidoamine. Said polyamidoamine is obtainable by reacting a diamine or a triamine, such as diethylenetriamine (or a mixture of two or more thereof), with the polycarboxylic acid, such as succinic acid, adipic acid, oxalic acid, phthalic acid, or a mixture of two or more thereof.

[0180] The term "polyazetidinium resin" may also be used and equally refers to the thermosetting resin that includes at least two azetidinium groups. An azetidinium group has the structure corresponding to formula (I) above.

[0181] A polyazetidinium resin can be an adduct of a halohydrin and a polyamine or polyamidoamine resin.

[0182] A polyazetidinium resin can be soluble or dispersible in water.

[0183] The crosslinker can be obtained by reacting e.g. a polyamidoamine resin with a halohydrin. In a specific variant, the halohydrin can be epichlorohydrin, epibromohydrin, or combinations thereof. The polyamidoamine resin can be obtained by reacting a polyamine and a polycarboxylic acid. The polyamine can be a polyalkylene polyamine. The polyalkylene polyamine is preferably a diethylenetriamine, triethylenetetramine, or combinations thereof.

[0184] Preferably, the polycarboxylic acid is a diacid, such as succinic acid, adipic acid, oxalic acid, phthalic acid, or mixtures of 2 or more thereof.

[0185] A polyazetidinium polymer can comprise a single polymer resin or a mixture of polymer resins resulting from the reaction of a halohydrin with a polyamidoamine.

[0186] The molar ratio of the polyamine(s) and of the polycarboxylic acid(s) can vary and the polyamidoamine resin can have terminal acid or primary amine functions.

[0187] The polyazetidinium polymer is preferably a reaction product of epichlorohydrin and of a polyamidoamine, wherein the polyamidoamine polymer can be obtained by reacting diethylenetriamine and adipic acid, see formula II below.

[0188] II:

[0189] Azetidinium group (AZR)

[0190] Where n represents the repeating unit in the polyazetidinium resin (PAE).

[0191] The polyazetidinium resin is preferably soluble in water. Thus, the polyazetidinium polymer composition used as crosslinker is preferably an aqueous polymer composition. The aqueous composition may e.g. be in the range of 10-50% by weight of the polyazetidinium resin in water. The present mineral fibre binder is based on a mixture of saccharides and proteins, which are crosslinked with the azetidinium functional crosslinker.

[0192] The unique crosslinking reactivity of the azetidinium functional crosslinker, in particular PAE, towards both proteins and saccharides is central to the presented binder technology. In brief, the electrophilic four membered azetidinium rings in the PAE resin can both self-crosslink and co-crosslink with the saccharides and proteins to generate covalent bonds. This occurs by nucleophilic attack on the a- position of the azetidinium ring of a nucleophile from the saccharide or protein leading to ring opening and formation of a covalent bond.

[0193] Compositions without saccharides all display very low wet strength even with high PAE contents. Compositions without protein, on the other hand, require high PAE levels (>9%) to achieve a satisfying level of unaged and aged strengths that are not significantly lower than PUF (comparative binder A).

[0194] Binder compositions made without an azetidinium functional crosslinker, such as PAE, display very low aged strengths which can be detrimental to e.g. an insulation product which has to maintain its mechanical strength over a long period, e.g. for decades. This illustrates the importance of including an azetidinium functional crosslinker, such as PAE. The strength results generally increase with increasing content of the azetidinium functional crosslinker, such as PAE. However, compositions displaying unaged and aged strengths at similar to or above prior art binders, such as PUF, can already be achieved with a very low amount of azetidinium functional crosslinker, such as PAE.

[0195] Thus, the binder composition comprises the azetidinium functional crosslinker such as PAE preferably in an amount of 1 -20% by weight of binder component solids, such as 1 .5-18 % by weight of binder component solids or preferably 2-16 % by weight of binder component solids or preferably 5-15% by weight of binder component solids. Binder component solids content - definition

[0196] The content by weight of each of the components in a given binder solution before curing is based on the anhydrous mass of the components, i.e. without solvents, in particular water. The following formula can be used:

[0197] In case of a PUF binder, formaldehyde and, if used, ammonia are also considered as components of the binder. While these starting materials are volatiles, they are reacted at least in part during the preparation of the PUF resin.

[0198] Binder solids - definition and procedure

[0199] The content by weight of binder after curing is termed “binder solids”.

[0200] Disc-shaped stone wool samples (diameter: 5 cm; height 1 cm) were cut out of stone wool and heat-treated at 590 °C for at least 30 minutes to remove all organics. The solids of a binder were measured by distributing a sample of the binder (approx. 2 g) onto a heat treated stone wool disc in a tin foil container. The tin foil container containing the stone wool disc was weighed before and directly after addition of the binder. Two such binder loaded stone wool discs in tin foil containers were produced and they were then heated for 1 h at 200 °C. After cooling and storing at room temperature for 10 minutes, the samples were weighed, and the binder solids were calculated as an average of the two results.

[0201] For the purpose of the present disclosure, the term “cured or partly cured binder” refers to a binder which has at least been cured to a certain degree, e.g. by thermally treating in a curing apparatus, but has not necessarily been treated to achieve full curing in all regions of the product. Accordingly, the term “cured or partly cured binder” for the purpose of the present disclosure includes binders containing cured and uncured regions.

[0202] Additives

[0203] The aqueous binder composition may further comprise one of more additives.

[0204] The one or more additives are preferably selected from a group of one or more pH adjusters, such as one or more bases and / or one or more acids; one or more hardener(s), coupling agents or adhesion promoter(s), such as a silane, such as an amino silane; one or more hydrophobic agents such as a silicone oil or silicone resin and / or fatty acid ester(s) of glycerol, one or more hydrofilic agents, one or more dust binding agent(s) such as oil(s), such as mineral oil(s), and / or one or more colouring agents.

[0205] The aqueous binder composition may comprise an additive selected from a group of mineral oils, silicone and / or silane and / or acids or bases or salts thereof.

[0206] Suitable pH adjusters may comprise bases or acids or a combination thereof. Suitable bases may comprise alkali metal or earth alkali metal hydroxides, e.g. lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium hydroxide or mixtures thereof. Less preferred bases could include ammonia or organic amines or alkali metal or earth alkali metal carbonates, since the use of ammonia or amine bases may increase emissions of ammonia, amines or nitrogen oxides and carbonate containing bases may release CO2 during mixing and / or curing. Suitable acids may include inorganic acids or organic acids. Examples of inorganic acids may include hydrochloric acid sulfuric acid, phosphoric acid. Examples of organic acids may include acetic acid, citric acid. The one or more additives may comprise one or more hydrophobic agents such as silicone and / or one or more mineral oil(s) and / or fatty acid ester(s) of glycerol.

[0207] The additives may be hydrophobic components such as one or more reactive or non-reactive silicones and may be added to the binder composition. Preferably, the one or more silicone reactive or non-reactive silicone compounds is selected from the group consisting of silicone constituted of a main chain composed of organosiloxane residues, especially diphenylsiloxane residues, alkylsiloxane residues, preferably dimethylsiloxane residues, bearing at least one hydroxyl, carboxyl or anhydride, amine, epoxy or vinyl functional group capable of reacting with at least one of the constituents of the binder composition.

[0208] The one or more hydrophobic component(s), such as silicone(s) are preferably present in an amount of 0.01 -1.5 weight-%, preferably from 0.01 -1.0 weight-%, more preferably 0.015 -0.5 weight-%, based on the MMVF content in the product.

[0209] Preferably the one or more additives may comprise one or more hardeners or adhesion promoters, or coupling agents such as a silane, such as an aminosilane. Increasing of silane content to above 0.6% only resulted in small to negligible further increases in the mechanical strengths.

[0210] Hardeners or adhesion promoters, such as silanes, such as aminosilanes are preferably present in an amount of 0.01 to 5 % by weight based on the binder component solids. Preferably, the one or more silane is an amino-functional silane such as Dynasylan®HYDROSIL 1151 from Evonik Industries or Silquest VS-142 from Momentive

[0211] Preferably, the silane, preferably aminosilane, is added to the binder composition, such as in an amount of 0.05-1.8 % by weight of binder component solids, preferably 0.1 -1 .0 % by weight of binder component solids or more preferred 0.1 - 0.6% % by weight of binder component solids. Silane plays an important role in improving the mechanical strength even further, especially in aged strength. With only 0.2% silane, a significant increase in both autoclave aged and water bath aged strengths is already seen, compared to without any silane added.

[0212] As mentioned above, one or more oil(s) may be added to the aqueous binder composition. The oils provide hydrophobicity to the mineral fibre product and also has the ability to adhere in the product dust that might be created during production of the mineral fibre product. The one or more oils may be selected from mineral oil(s) such as BS 30 / 90, LOTUS group and / or one or more fatty acid ester(s) of glycerol.

[0213] The fatty acid ester content is preferably 0.6 to 30, more preferably 1 to 10, more preferably 2 to 7.5 % by weight, based on the binder component solids.

[0214] The at least one fatty acid ester of glycerol is preferably selected from one or more components from the group consisting of linseed oil, coconut oil, corn oil, canola oil, cottonseed oil, olive oil, palm oil, peanut oil (ground nut oil), rapeseed oil, including canola oil, safflower oil, sesame oil, soybean oil, sunflower oil or combinations thereof.

[0215] A fatty acid is a carboxylic acid with an aliphatic chain, which is either saturated or unsaturated.

[0216] Glycerol is a polyol compound having the IUPAC name propane-1 , 2, 3-triol.

[0217] Naturally occurring fats and oils are glycerol esters with fatty acids (also called triglycerides).

[0218] The term fatty acid ester of glycerol refers to mono-, di-, and tri-esters of glycerol with fatty acids. While the term fatty acid can in the present context be any carboxylic acid with an aliphatic chain, it is preferred that it is carboxylic acid with an aliphatic chain having 4 to 28 carbon atoms, preferably of an even number of carbon atoms. Preferably, the aliphatic chain of the fatty acid is unbranched.

[0219] The at least one fatty acid ester of glycerol is maybe in form of a plant oil and / or animal oil. The term "oil" comprises at least one fatty acid ester of glycerol in the form of oils or fats.

[0220] Preferably, the at least one fatty acid ester of glycerol is a plant- based oil.

[0221] The at least one fatty acid ester of glycerol is preferably used in in form of fruit pulp fats such as palm oil, olive oil, avocado oil; seed-kernel fats such as lauric acid oils, such as coconut oil, palm kernel oil, babassu oil and other palm seed oils, other sources of lauric acid oils; palmitic-stearic acid oils such as cocoa butter, shea butter, borneo tallow and related fats (vegetable butters); palmitic acid oils such as cottonseed oil, kapok and related oils, pumpkin seed oil, corn (maize) oil, cereal oils; oleic-linoleic acid oils such as sunflower oil, sesame oil, linseed oil, perilla oil, hempseed oil, teaseed oil, safflower and niger seed oils, grape-seed oil, poppyseed oil, leguminous oil such as soybean oil, peanut oil, lupine oil; cruciferous oils such as rapeseed oil, mustard seed oil; conjugated acid oils such as tung oil and related oils, oiticica oil and related oils; substituted fatty acid oils such as castor oil, chaulmoogra, hydnocarpus and gorli oils, vernonia oil; animal fats such as land-animal fats such as lard, beef tallow, mutton tallow, horse fat, goose fat, chicken fat; marine oils such as whale oil and fish oil or mixtures thereof.

[0222] More preferred, the at least one fatty acid ester of glycerol is in form of a plant oil, in particular selected from one or more components from the group consisting of linseed oil, coconut oil, corn oil, canola oil, cottonseed oil, olive oil, palm oil, peanut oil (ground nut oil), rapeseed oil, including canola oil, safflower oil, sesame oil, soybean oil, sunflower oil or mixtures thereof.

[0223] In one variant the at least one fatty acid ester of glycerol is not of natural origin.

[0224] In one variant, the at least one fatty acid ester of glycerol is a modified plant or animal oil.

[0225] The at least one fatty acid ester of glycerol may comprise at least one trans-fatty acid.

[0226] Alternatively, the at least one fatty acid ester of glycerol is in form of an animal oil, such as a fish oil.

[0227] The content of fatty acid ester of glycerol may be 0.6 to 30, such as 1 to 10, such as 2 to 7.5 wt.-percent based on binder component solids.

[0228] The additives can be added before or after mixing of the final aqueous binder composition. Alternatively, additives can be added inline and mixed with the aqueous binder composition shortly before or while being dosed to the MMVF fibres. Alternatively, additive(s) can be added via separate applications means, e.g. spray nozzles, in parallel to the application of the aqueous binder composition to the MMVF fibres.

[0229] A method of producing a mineral fibre product

[0230] The present disclosure is also directed to a method of producing a bonded mineral fibre product, which comprises the steps of contacting mineral fibres with an aqueous binder composition according to the disclosure and curing the binder to form a cured mineral fibre product comprising a biodegradable binder. The aqueous binder composition and the components thereof has been described above. All indications discussed above for the aqueous binder composition of course also apply to the aqueous binder composition used in the method of the present disclosure.

[0231] The mineral fibres employed may be for instance any of man-made vitreous fibres (MMVF), glass fibres or glass wool, ceramic fibres, basalt fibres, slag fibres, stone fibres or stone wool and others. The mineral fibres are preferably of the types generally known as rock, stone or slag fibres, most preferably stone fibres. These fibres may be present as a wool product, e.g. like a stone wool product.

[0232] The man-made vitreous fibres can have any suitable oxide composition.

[0233] Stone fibres typically comprise the following oxides, in percent by weight:

[0234] SiO2: 30 to 51

[0235] AI2O3: 12 to 25

[0236] CaO: 8 to 30

[0237] MgO: 2 to 25

[0238] Fe2Os: 2 to 15

[0239] Na2O+K2O: not more than 10

[0240] CaO+MgO: 10 to 30

[0241] In the above, the iron oxide may be a mixture of FeO and Fe2Os but is quoted herein as Fe2O3.

[0242] The man-made vitreous fibres preferably have the following levels of elements, calculated as oxides in wt%:

[0243] SiO2: at least 30, 32, 35 or 37; not more than 51 , 48, 45 or 43

[0244] AI2OS: at least 12, 16 or 17; not more than 30, 27 or 25

[0245] CaO: at least 8 or 10; not more than 30, 25 or 20

[0246] MgO: at least 2 or 5; not more than 25, 20 or 15

[0247] FeO (including Fe2O3): at least 4 or 5; not more than 15, 12 or 10 FeO+MgO: at least 10, 12 or 15; not more than 30, 25 or 20

[0248] Na2O+K2O: zero or at least 1 ; not more than 10

[0249] CaO+MgO: at least 10 or 15; not more than 30 or 25

[0250] TiC : zero or at least 1 ; not more than 6, 4 or 2

[0251] TiO2+FeO: at least 4 or 6; not more than 18 or 12

[0252] B2O3: zero or at least 1 ; not more than 5 or 3

[0253] P2O5: zero or at least 1 ; not more than 8 or 5

[0254] Others: zero or at least 1 ; not more than 8 or 5

[0255] Glass fibres typically comprise the following oxides, in percent by weight:

[0256] SiO250 to 70

[0257] AI2O3 10 to 30

[0258] CaO not more than 27

[0259] MgO not more than 12

[0260] Glass fibres can also contain the following oxides, in percent by weight: Na2O+K2O 8 to 18, in particular Na2O+K2O greater than CaO+MgO, and B2O3 3 to 12.

[0261] Some glass fibre compositions can contain AI2O3 less than 2%.

[0262] The mineral fibres preferably have a geometric fibre diameter of 1 -6 pm, such as 1 -5 pm, or preferably 1 -4 pm or preferably 1 -2 pm.

[0263] The method of producing a bonded mineral fibre product preferably comprises the steps of:

[0264] - making a melt of raw materials,

[0265] - fiberizing the melt by means of a fibre forming apparatus to form mineral fibres, wherein the mineral fibres formed are preferably directed into a spinning chamber,

[0266] - providing the mineral fibres in the form of a collected web, - applying the aqueous binder composition on the mineral fibres before, during or after the provision of the collected web to form a mixture of mineral fibres and binder composition, wherein the aqueous binder composition is preferably applied by spraying before the provision of the collected web, preferably in the spinning chamber

[0267] - curing the binder composition mixed with the mineral fibres.

[0268] Man-made vitreous fibres can be made from a mineral melt. A mineral melt is provided in a conventional manner by providing mineral materials and melting them in a furnace. This furnace can be any of the types of furnaces known for production of mineral melts for man-made vitreous fibres, for instance a shaft furnace such as a cupola furnace, a tank furnace, a submerged electrical furnace, or a cyclone furnace.

[0269] Any suitable method may be employed to form man-made vitreous fibres from the mineral melt by fiberization. The fiberization can be by a spinning cup process in which melt is centrifugally extruded through orifices in the walls of a rotating cup (spinning cup, also known as internal centrifugation). Alternatively, the fiberization can be by centrifugal fiberization by projecting the melt onto and spinning off the outer surface of one fiberizing rotor, or off a cascade of a plurality of fiberizing rotors, which rotate about a substantially horizontal axis (cascade spinner).

[0270] The melt is thus formed into a cloud of fibres entrained in air and the fibres are collected as a web on a conveyor and carried away from the fiberizing apparatus. The web of fibres is then consolidated, which can involve cross-lapping and / or longitudinal compression and / or vertical compression and / or winding around a mandrel to produce a cylindrical product for pipe insulation. Other consolidation processes may also be performed, such as producing granulates.

[0271] The step of contacting the mineral fibres with the aqueous binder composition can be effected by applying the aqueous binder composition on the mineral fibres with conventional means, for instance by spraying. The amount of binder and / or additive may be the same for each spinner or it may be different.

[0272] The binder composition is applied to the fibres preferably when they are a cloud entrained in air. Alternatively, it can be applied after collection on the conveyor, but this is less preferred.

[0273] As used herein, the term "collected web" is intended to include any mineral fibres that have been collected together on a surface, i.e. they are no longer entrained in air, e.g. the fiberized mineral fibres, granulate, tufts or recycled web waste. The collected web could be a primary web that has been formed by collection of fibres on a conveyor belt and provided as a starting material without having been crosslapped or otherwise consolidated.

[0274] Alternatively, the collected web could be a secondary web that has been formed by crosslapping, or otherwise consolidating a primary web, e.g. as described above. Preferably, the collected web is a primary web.

[0275] In a variant of the method, the binder may be mixed with the mineral fibres after the provision of the collected web in the following steps:

[0276] - subjecting the collected web of mineral fibres to a disentanglement process,

[0277] - suspending the mineral fibres in a primary air flow,

[0278] - mixing binder composition with the mineral fibres before, during or after the disentanglement process to form a mixture of mineral fibres and binder.

[0279] The disentanglement process comprises feeding the collected web of mineral fibres from a duct with a lower relative air flow to a duct with a higher relative air flow. In this variant, the disentanglement is believed to occur, because the fibres that enter the duct with the higher relative air flow first are dragged away from the subsequent fibres in the web. This type of disentanglement is particularly effective for producing open tufts of fibres, rather than the compacted lumps that can result in an uneven distribution of materials in the product.

[0280] According to a particularly preferred variant of the method, the disentanglement process comprises feeding the collected web to at least one roller which rotates about its longitudinal axis and has spikes protruding from its circumferential surface. The rotating roller will usually also contribute at least in part to the higher relative airflow. Often, rotation of the roller is the sole source of the higher relative air flow.

[0281] The mineral fibres and optionally the binder may be fed to the roller from above. It is also preferred for the disentangled mineral fibres and optionally the binder to be thrown away from the roller laterally from the lower part of its circumference. Preferably, the mineral fibres are carried approximately 180 degrees by the roller before being thrown off.

[0282] The binder may be mixed with the mineral fibres before, during or after the disentanglement process. It is preferred to mix the binder with the fibres prior to the disentanglement process.

[0283] It is also feasible that the binder be pre-mixed with a collected web of mineral fibres before the disentanglement process. Further mixing could occur during and after the disentanglement process. Alternatively, the binder could be supplied to the primary air flow separately and mixed in the primary air flow.

[0284] The mixture of mineral fibres and binder is collected from the primary air flow by any suitable means. The primary air flow is preferably directed into the top of a cyclone chamber, which is open at its lower end and the mixture is collected from the lower end of the cyclone chamber. The mixture of mineral fibres and binder is preferably thrown from the disentanglement process into a forming chamber.

[0285] Having undergone the disentanglement process, the mixture of mineral fibres and the binder may be collected, consolidated and cured. Preferably, the mixture of mineral fibres and the binder is collected on a foram inous conveyor belt having suction means positioned below it.

[0286] The method may be performed as a batch process. However, the preferred method is performed at a MMVF production line feeding a primary or secondary MMVF web to the consolidation step before curing, which provides a particularly cost efficient and versatile method to provide MMVF products having favourable mechanical properties and thermal insulation properties in a wide range of densities.

[0287] After consolidation, the consolidated web of fibres is passed into a curing device to cure the binder.

[0288] The curing process may commence immediately after application of the binder to the fibres. The curing is defined as a process whereby the binder composition undergoes a physical and / or chemical reaction, which in case of a chemical reaction usually increases the molecular weight of the compounds in the binder composition and thereby increases the viscosity of the binder composition, usually until the binder composition reaches a solid state. The cured binder composition binds the fibres to form a structurally coherent matrix of fibres.

[0289] The curing process preferably comprises drying by pressure. The pressure may be applied by blowing air or gas through and / or over the mixture of mineral fibres and binder. In a variant, the curing process comprises a drying process. For example, the curing process comprises drying by pressure. The pressure may be applied by blowing air or gas to the mixture of mineral fibres and binder. The blowing process may be accompanied by heating or cooling, or it may be at ambient temperature.

[0290] The curing preferably takes place in a curing device such as in a conventional curing oven or a heat press.

[0291] The curing of a binder composition in contact with the mineral fibres in a heat press has the particular advantage that it enables the production of high-density products.

[0292] The curing of the aqueous binder composition, which is in contact with the mineral fibres can be carried out within a wide temperature range. Preferably, the curing is carried out at temperatures from 180 to 280°C, preferably at temperatures from 200 to 270°C, more preferably at temperatures from 220 to 265°C.

[0293] For example, the curing takes place for a time of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.

[0294] Typically, curing takes place at a temperature of 160-280 °C for a time of 30 seconds to 20 minutes. These curing conditions may result in a core temperature in the MMVF product of up to 250°C which is sufficient for curing the binder throughout the MMVF product.

[0295] The aqueous binder composition is preferably applied in the close vicinity of the fibre forming apparatus, such as a cascade spinning apparatus or a cup spinning apparatus, in either case immediately after the fibre formation. Thus, the aqueous binder composition is preferably applied to the mineral fibers formed in the spinning chamber, preferably by spraying. The fibres with applied binder are thereafter usually conveyed onto a conveyor belt as a web, such as a collected web. The web, such as a collected web may be subjected to longitudinal or length compression after the fibre formation and before substantial curing has taken place.

[0296] There are various types of centrifugal spinners used as a fibre forming apparatus for fiberizing mineral melts.

[0297] A conventional centrifugal spinner is a cascade spinner, which comprises a sequence of a top (or first) rotor and a subsequent (or second) rotor and optionally other subsequent rotors (such as third and fourth rotors). Each rotor rotates about a different substantially horizontal axis with a rotational direction opposite to the rotational direction of the or each adjacent rotor in the sequence. The different horizontal axes are arranged such that melt which is poured on to the top rotor is thrown in sequence on to the peripheral surface of the or each subsequent rotor, and fibres are thrown off the / or each subsequent rotor, and optionally also off the top rotor.

[0298] For example, a cascade spinner or other spinner is arranged to fiberize the melt, and the fibres are entrained in air as a cloud of the fibres.

[0299] Many fibre forming apparatuses comprise a disc or cup that spins around a substantially vertical axis. It is then conventional to arrange several of these spinners in-line, i.e. substantially in the first direction, for instance as described in GB-A-926,749, US-A-3,824,086 and WO-A-83 / 03092.

[0300] There is usually a stream of air associated with the one or each fiberizing rotor whereby the fibres are entrained in this air as they are formed off the surface of the rotor. Preferably, the aqueous binder composition and / or additives are added to the cloud of fibres by known means. The amount of binder and / or additive may be the same for each spinner or it may be different.

[0301] As used herein, the term "collected web" is intended to include any mineral fibres that have been collected together on a surface, i.e. they are no longer entrained in air, e.g. the fiberized mineral fibres, granulate, tufts or recycled web waste. The collected web could be a primary web that has been formed by collection of fibres on a conveyor belt and provided as a starting material without having been crosslapped or otherwise consolidated.

[0302] Alternatively, the collected web could be a secondary web that has been formed by cross-lapping or otherwise consolidating a primary web. Preferably, the collected web is a primary web.

[0303] Mineral fibre product

[0304] The present disclosure is also directed to a mineral fibre product comprising mineral fibres bound by a biodegradable binder resulting from the curing of an aqueous binder composition according to the present disclosure. The mineral fibre product is preferably obtainable by the method according to the disclosure.

[0305] The aqueous binder composition and the method have been described above. All indications discussed above for the aqueous binder composition and the method such as the mineral fibres also apply to the mineral fibre product.

[0306] The density of the mineral fibre product is preferably in the range of 10-1200 kg / m3, such as 30-800 kg / m3, such as 40-600 kg / m3, such as 50-250 kg / m3, such as 60-200 kg / m3. Preferably, the mineral fibre product is an insulation product, such as a thermal or acoustical insulation product, in particular having a density of 10 to 200 kg / m3

[0307] The loss on ignition (LOI) of the mineral fiber product is preferably within the range of 0.1 to 25.0 %, such as 0.3 to 18.0 %, such as 0.5 to 12.0 %, such as 0.7 to 8.0 % by weight or more preferred as 1 .0 to 6.0 % by weight.

[0308] The preferred cured mineral fibre product has an average density of 75-85 kg / m3(according to EN ISO 29470:2020) and one or more of:

[0309] - a compression strength, such as unaged compression strength, at 10% o10 (kPa) according to EN ISO 29469:2022 greater than or equal to 15 kPa, such as greater than or equal to19 kPa and / or

[0310] - a delamination strength, such as unaged delamination strength, omt greater than or equal to 7.5 kPa, such as greater than or equal to 10 kPa, according to EN 1607.

[0311] The mineral fibre product can be in any conventional configuration, for instance a mat or slab, and can be cut and / or shaped (e.g. into pipe sections) before, during or after curing of the binder. The mineral fibre product can thus be a granulate or a shaped product, such as a slab, a pad or a blanket, a rolled-up blanket or a shaped item, such as a tubular segment.

[0312] Applications

[0313] The present disclosure is also directed to the use of an aqueous binder composition according to the present disclosure as described above for the production of a mineral fibre product.

[0314] The present disclosure is also directed to the use of an aqueous binder composition according to the present disclosure as described above for lowering the formaldehyde and / or ammonia and / or phenol emissions during production of a mineral fibre product.

[0315] The use is preferably carried out in a method according to the disclosure as described above.

[0316] The present disclosure is also directed to a method of reducing the formaldehyde emission and / or the ammonia emission and / or phenol emission is preferably a method of producing a mineral fibre product according to the disclosure.

[0317] The present disclosure is also directed to a use of an inventive aqueous binder composition in the production of formaldehyde free mineral fibre products where the emission is below 5 pg / m2 / h of formaldehyde from the mineral fibre product, preferably below 3 pg / m2 / h, when measured in accordance with ISO 16000 - 1 :2004.

[0318] The aqueous binder composition, the method and the mineral fibre product according to the present disclosure have been described above.

[0319] The present disclosure is also directed to a use of an inventive aqueous binder composition in the production of formaldehyde free mineral fibre products, where the cured MMVF binder is biodegradable- after curing - such as able to be decomposed at least 20% within a period of 45 days when composted under aerobic conditions at 58°C according to ISO 14855-1 (2012) (standard test variant, i.e. without vermiculite bed).

[0320] The aqueous binder composition, the method and the mineral fibre product according to the present disclosure have been described above. The drawings

[0321] In the examples described below, several binder compositions which fall under the definition of the present disclosure were prepared. The mechanical properties, binder solubility and / or biodegradability of the cured binder(s) are also investigated in the examples below and the results are shown in figs. 1 -19.

[0322] Examples

[0323] In the following examples, several binders which fall under the definition of the present disclosure were prepared and compared to binders according to the prior art.

[0324] Unless specifically stated otherwise all amounts in % specified above and / or below are % by weight of binder component solids.

[0325] Experimental methods and definitions

[0326] Materials

[0327] Proteins, collagen-type: 0 bloom technical gelatine (CamGlue Moreu), 80-100 bloom technical gelatine (CamGlue Moreu), 150-180 bloom technical gelatine (CamGlue Moreu), partially hydrolyzed technical gelatine (3 kDa, CamGlue Moreu), marine collagen (3 kDa, MM Ingredients), Gelita NOVOTECH CB800 gelatin product (3 kDa, GELITA AG)

[0328] Proteins, non-collagen type: crespotec bind gluten (Crespel-Deiters), whey protein isolate (Aria, SP-9226), egg albumin (hen egg albumin powder, Eggs Product), gliadin (Sigma-Aldrich, G3375), modified gluten (Crespel-Deiters), soybean flour (type I, Sigma-Aldrich, S9633), Spirulina algae protein (UnikFood).

[0329] Saccharides: 75 wt.% aq. glucose syrup (Cargill), D-(+)-glucose monohydrate (Millipore, 49159), D-(-)-fructose (Sigma-Aldrich, 102676768), D-(+)-galactose (Sigma-Aldrich, G0750), D-(+)-mannose (Sigma-Aldrich, M8574), D-(+)-xylose (Sigma-Aldrich, W360600), L-(+)-arabinose (TCI, A0515), L-(+)-rhamnose monohydrate (TCI, R0013), D-(-)-ribose (TCI, R0025), sucrose (Sigma-Aldrich, S9378), D-(+)-melezitose monohydrate (Sigma-Aldrich, 63620), D-(+)-lactose monohydrate (Sigma-Aldrich, 61339), D-(+)-raffinose pentahydrate (Sigma- Aldrich, R0250), D-(+)-maltose monohydrate (Sigma-Aldrich, 63418), maltotriose hydrate (Sigma-Aldrich, 851493), maltodextrin (DE = 15-20, Sigma-Aldrich, 419680), maltodextrin (DE = 4-7, Sigma-Aldrich, 419672).

[0330] Crosslinker: 20 wt.% PAE (polyamide epichlorohydrin resin Solenis Kymene

[0331] GHP20).

[0332] Other reagents 40 wt.% silane (Momentive Silquest® VS-142 oligomeric amino silane in water). For application in lab, the silane solution was diluted to 4 wt.% before usage. For application in production, no dilution is needed. Isophthalaldehyde (115282), glyoxal (40 wt.% in water, 128465), and tannin (403040) were purchased from Sigma-Aldrich. Sodium hydroxide (NaOH) pellet (567530) was purchased from Sigma-Aldrich. For application in lab, sodium hydroxide was used as a 1 mol / L solution, which was prepared by dissolving 40 g NaOH pellets in 1 L water. For application in production, 27.65% NaOH solution

[0333] (Brenntag, 6743) was used. All components for which a concentration is not detailed above were assumed completely pure and anhydrous for simplicity.

[0334] Weibulls® Blomsterjord (Econova Garden AB) was purchased from a local construction market and used as the standard soil for biodegradation test. The soil has a pH of 5.5-6.3 and conductivity of 15-35 mS / m. Microcrystalline cellulose (20 pm, Sigma-Aldrich 310697) was used as a positive reference in all the biodegradation tests. 3 mol / L NaOH solution was used to absorb CO2 produced during biodegradation, which was prepared by dissolving 360 g NaOH pellets in 3 L water. Thymolphthalein (Sigma-Aldrich 1081750005) was dissolved in the NaOH solution to reach a concentration of 0.4 wt.%, which works as a pH indicator.

[0335] General methods

[0336] Measurements of pH were performed using a Mettler Toledo SevenCompactTM S220 pH meter equipped with a Mettler Toledo InLab® Expert Pro-ISM pH electrode and temperature probe. Crude stone shots (predominantly sphere particles that have the same chemical composition as the stone wool fibers) formed during the cascade spinning process of a stone melt in the production of stone wool fibers were obtained from a ROCKWOOL factory in the Netherlands. Cleaned and sifted stone shots appropriate for the manufacture of composite bars were produced from these crude stone shots by ProChem GmbH, Germany. In brief, the stone shots were heat treated overnight at 590 °C to remove any traces of organic matter. After cooling, the stone shots were sifted through 0.50 mm and 0.25 mm sieves. The coarse and fine fractions were discarded, and the remaining stone shots (particle size between 250 and 500 pm) were washed thoroughly several times in demineralized water. The sifted and cleaned stone shots were dried and then stored in a closed bag until use. In the following stone shots obtained are simply termed shots. All the results were obtained using the same batch of shots.

[0337] A Kenwood KCC90 Cooking Chef mixing machine with induction heating capacity was used for mixing shots and binders for the manufacture of composite bars.

[0338] Heat resistant silicone forms for the preparation of composite bars (4x5 slots per form; slot top dimension: length = 5.6 cm, width = 2.5 cm; slot bottom dimension: length = 5.3 cm, width = 2.2 cm; slot height = 1.1 cm) were customized from Dongguan Linkaiz Crafts Gifts Co, Ltd.

[0339] Three-point bending tests were recorded on a Bent Tram SUT 3000 / 520 test machine (test speed: 10.0 mm / min; rupture level: 50 N; nominal strength: 30 N / mm2; support distance: 40 mm; max deflection 20 mm; nominal E-modulus 10000 N / mm2). The bars were placed with the “top face” up (i.e. the face with the dimensions length = 5.6 cm, width = 2.5 cm) in the machine.

[0340] Tin foil containers used to measure of binder solids and loss on ignition of composite bars were pre-treated by heating at 590 °C for 15 minutes prior to use to remove all organics. Binder component solids content - definition

[0341] The content by weight of each of the components in a given binder solution before curing is based on the anhydrous mass of the components, i.e. without solvents, in particular water. The following formula can be used: binder component A solids (j ) + binder component B solids (j ) + •••

[0342] Binder component solids content (%) = - x 100% total weight of mixture (g)

[0343] In case of calculating the binder component solids of a single binder component, e.g. dextrose only, the binder component A will be dextrose.

[0344] In case of calculating the binder component solids content of a saccharide mixture in any of the given binders comprising saccharide, A can be e.g. dextrose and B can be e.g. fructose.

[0345] In case of calculating the binder component solids content of e.g. an additive, A can be the additive, B can be a saccharide, e.g. dextrose, and C can be protein, e.g. gelatine.

[0346] In case of a PUF binder, for example, formaldehyde and ammonia are also considered as component solids of the binder. While these starting materials are volatiles, they are reacted at least in part during the preparation of the PUF resin.

[0347] Binder solids - definition and procedure

[0348] The content of binder after curing is termed “binder solids”.

[0349] Small samples of heat-treated stone wool (heat-treated at 590 °C for at least 30 minutes to remove all organics) were placed in three small tin foil containers (approx. 2 g heat-treated stone wool in each). A sample of the binder mixture (approx. 2 g) was distributed onto the heat-treated stone wool in each container. The tin foil containers containing the heat-treated stone wool were weighed before and directly after addition of the binder mixture. The samples were then treated at the times and temperatures detailed in the examples and tables. After cooling and storing at room temperature for 10 minutes, the samples were weighed, and the binder solids were calculated as an average of the three results. Afterwards the binder solids content is expressed in weight percent.

[0350] Reaction loss - definition

[0351] The reaction loss is defined as the difference between the binder component solids content and the binder solids.

[0352] Manufacture of composite bars

[0353] A binder solution with 20-25% binder component solid content was prepared as described in the examples. A known amount of the binder solution was then added to shots (460 g) in the Kenwood kitchen mixer at room temperature. With a targeting LOI of 2.67% in the shots, the amount of binder added to shots is dependent on the binder component solid content of the binder solution. After mixing slowly for 3 minutes, the resulting mixture was pressed into a silicon mold to make 16 bars. Afterwards, the mold was put into a pre-heated oven to cure. The curing temperature and curing time were indicated in the examples. After curing, the bars were cooled down to room temperature and stored in a climate chamber at 22 °C with 50% relative humidity.

[0354] Ageing treatment of composite bars

[0355] Ageing treatment of composite bars was performed by subjecting the bars to autoclave treatment (15 min / 120 °C / 1 .2 bar) or water bath treatment (3 h / 80 °C), followed by cooling down to room temperature. After initial drying at ambient conditions for one day, the composite bars were then transferred to a climate chamber at 22 °C / 50% relative humidity for at least 3 more days to be dry.

[0356] Measurement of mechanical strengths of unaged, autoclave aged or water bath aged composite bars The maximum load force required to break composite bars was recorded in a three-point bending test. For each data point, an average value was calculated on the basis of four bars that had been subjected to identical treatment.

[0357] Measurement of loss on ignition (LOI) of composite bars

[0358] Loss on ignition (LOI) of the composite bars was measured in small tin foil containers by heat treatment at 590 °C for 1 h. The tin foil container was first weighed (wi, g), and then four bars (usually after being broken in the three-point bending test) were placed into the tin foil container. The ensemble was weighed (W2, g) and then placed in an oven at 590 °C for 1 h to bum off all the organics. After cooling down to room temperature, the weight of the ensemble was recorded (ws, g) again and the LOI was calculated as the following:

[0359] W?— Wo

[0360] LOI (%) = — - - x 100% w2— wx

[0361] Binder solubility

[0362] Binder solubility is defined as the weight percentage of the binder that was dissolved during the water bath aging (80 °C for 3 h), and it is calculated as the following: water bath aged

[0363] Aerobic biodegradation study in the lab:

[0364] Binder sample preparation:

[0365] A binder solution with 20-25% binder component solid content was first prepared as described in the examples. Instead of mixing with the shots, the thus-prepared binder solution was transferred into an aluminum container (18 cm*13 cm *5 cm) and cured in a pre-heated oven. The curing condition (temperature and time) was the same as for the composite bars. After cooling down to room temperature, the cured binder was milled into fine powder (< 40 pm) with a Retsch RS200 Vibratory Disc Mill (RETSCH GmbH). The powder was collected and used for biodegradation test.

[0366] Aerobic biodegradation in soil at room temperature:

[0367] Aerobic biodegradation in soil was performed with a Gas Endeavour® III instrument (BPC Instruments AB, Sweden), which measures the biodegradation of a sample in inoculum by monitoring the accumulated O2 consumption over time. Prior to the test, the soil used for the test was first sieved through a 3.55 mm sieve manually to remove the large debris. Then, 1 g binder powder was mixed homogeneously with 100 g of the sieved soil, which was then loaded into the reactor. Each sample was prepared as duplicate. For each test, a blank control, namely, 100 g soil without any binder added, and a positive control, namely, 100 g soil with 1 g microcrystalline cellulose (20 pm), were prepared. The O2 consumption in a blank sample was used as the baseline, which was to be deducted to calculate the net O2 consumption of each sample. The positive control was to ensure the biological activity of the soil used, as cellulose has been long proven an easily biodegradable polymer. The reactors were placed in an incubator to keep the temperature constant at 25 °C. For quick screening purposes, the tests were stopped once a clear trend was seen and the O2 consumption curve reached a stable plateau (normally after 4 weeks). It is worth mentioning that the net O2 consumption is not equivalent to biodegradation degree. For each sample, the chemical composition (the amount of carbon, hydrogen, oxygen, etc.) determines the theoretical amount of O2 that could be consumed if the sample is 100% biodegradable. However, the net O2 consumption could give us an indication whether the sample is biodegradable or not, if yes, how fast or slow it biodegrades. Also importantly, since the O2 consumption is also largely dependent on the microbial activity of the soil, it is not reasonable to compare the results from different runs of experiments. During our experiments, we noticed that the soil activity changes from batch to batch. Even with the same batch of soil, the activity of the soil gets lower and lower overtime. For the same sample, higher net O2 consumption is always seen in experiments with freshly bought soil than experiments with soil that has been standing at room temperature for a long period of time (weeks to months). This is most likely caused by the slow reduction of active microorganisms during storage.

[0368] Aerobic biodegradation test under static controlled composting conditions

[0369] Once the samples tested in lab showed certain level of biodegradation, some were chosen to send externally to further confirm the results. The biodegradation tests were done externally at Normec OWS (Ghent, Belgium) under standard room temperature (25 ± 2 °C) following the standard ISO 17556:2019 “Plastics - Determination of the ultimate aerobic biodegradability in soil by measuring the oxygen demand in a respirometer or the amount of carbon dioxide evolved (2019)”, or under composting conditions (58 ± 2 °C) following the standard ISO 14855-1 (2012) “Determination of the ultimate aerobic biodegradability of plastic materials under controlled composting conditions - Method by analysis of evolved carbon dioxide (2012)”, but in duplicate instead of triplicate. For the former, 2 g binder powder was added to 500 g soil inoculum and incubated in the dark at ambient room temperature for 120 days. For the latter, 4 g binder powder was added to 60 g compost inoculum and incubated at 58 ± 2 °C for 45 days.

[0370] Measurements of simulated spinning chamber emissions

[0371] Immediately prior to commencing each emission measurement, approximately 0.70 g of the binder mixture was distributed evenly on binder-free stone wool samples in a small ceramic crucible. Background emissions were obtained by starting the emission measurements in the oven heated to 95 °C a few minutes before inserting the sample. The sample was then loaded into the tube oven and a temperature probe was inserted close to the sample to measure the actual temperature. Gas phase emissions IR spectra were then recorded with a 5 second sample frequency during a period of about 1 hour at 95 °C. The recorded individual emission concentration time series obtained from the start of the measurement to the disappearance of the signal from water evaporation (generally about 40 minutes) were integrated to yield the simulated spinning chamber emissions of components such as ammonia, methanol, carbon dioxide, formaldehyde, phenol, isocyanic acid, acetaldehyde, acetic acid, carbon monoxide, formic acid, furfural, and urea. Two measurements were performed for each binder composition and the emission results were averaged.

[0372] Measurements of simulated curing emissions

[0373] The simulated curing emissions were obtained in an analogous manner to the simulated spinning chamber emissions. However, the samples were first either subjected to measurement of simulated spinning chamber emissions or to a similar treatment in an oven (1 hour at 95 °C). The measurements were recorded at the curing temperatures and times same as in mini-bar curing, with the background emissions obtained at the same temperatures for a few minutes prior to inserting the sample. The recorded individual emission concentration time series obtained during the measurement were integrated to yield the simulated curing emissions of components such as ammonia, isocyanic acid, carbon dioxide, acetic acid, carbon monoxide, formaldehyde, formic acid, furfural, hydrogen cyanide, methane, and sulfur dioxide. Two measurements were performed for each binder composition and the emission results were averaged.

[0374] Comparative binder compositions from the prior art

[0375] Comparative binder A (phenol-formaldehyde resin modified with urea, a PUF- resol)

[0376] A phenol-formaldehyde resin is prepared by reacting 37% aq. formaldehyde (606 g) and phenol (189 g) in the presence of 46% aq. potassium hydroxide (25.5 g) at a reaction temperature of 84°C preceded by a heating rate of approximately 1 °C per minute. The reaction is continued at 84 °C until the acid tolerance of the resin is 4 and most of the phenol is converted. Urea (241 g) is then added and the mixture is cooled.

[0377] The acid tolerance (AT) expresses the number of times a given volume of a binder can be diluted with acid without the mixture becoming cloudy (the binder precipitates). Sulfuric acid is used to determine the stop criterion in a binder production and an acid tolerance lower than 4 indicates the end of the binder reaction. To measure the AT, a titrant is produced from diluting 2.5 mL cone, sulfuric acid (>99 %) with 1 L ion exchanged water. 5 mL of the binder to be investigated is then titrated at room temperature with this titrant while keeping the binder in motion by manually shaking it; if preferred, use a magnetic stirrer and a magnetic stick. Titration is continued until a slight cloud appears in the binder, which does not disappear when the binder is shaken.

[0378] The acid tolerance (AT) is calculated by dividing the amount of acid used for the titration (mL) with the amount of sample (mL):

[0379] AT = (Used titration volume (mL)) I (Sample volume (mL))

[0380] Using a portion of the urea-modified phenol-formaldehyde resin obtained (100.0 g), a binder is made by addition of 28% aq. ammonia (7.47 g) and ammonium sulfate (1 .20 g) followed by water (100.9 g). The binder solids were then measured as described above: 22.0% for 1 h at 200 °C (thus 30.2% reaction loss). The mixture was then diluted with the required amount of water and 4% Momentive VS-142 silane (17.5% or 20% final binder solids solution, 0.2% silane of binder solids; final pH 9.6).

[0381] Binder compositions according to the present disclosure

[0382] The core issue we are trying to solve in this invention is to develop binder which is a biodegradable / industrially compostable. Biodegradability refers to the natural breakdown of materials, while compostability refers to the biodegradation of materials under specific conditions. For simplicity, the term ’’biodegradability” is used hereafter) binder with good mechanical properties for stone wool applications. The essential challenges for this new binder are to obtain sufficiently high mechanical strength, while maintaining a high degree of biodegradability. To meet the biodegradability requirements, e.g. in order to obtain an official certificate under one or more certification programs, it is typically required that the binder component can be shown to have either absolute or relative 90% biodegradation within the test period). Thus, the amount of the three main ingredients of this new binder - non-plant-based protein (exemplified using gelatine), saccharides, and PAE, must be carefully regulated to obtain the desired degree of biodegradation. A binder based on saccharides crosslinked with PAE is not biodegradable, PAE itself is not biodegradable while proteins, e.g. non-plant-based protein, in particular gelatin, are highly biodegradable. Thus, the only biodegradable component in the present binder system is protein / gelatin. Therefore, the protein / gelatin amount should be relatively high to ensure high biodegradability, while maintaining a high mechanical strength. Thus, the binder component solid content of non-plant-based protein, - here exemplified mainly with gelatine - is preferably above 80%.

[0383] Example 1 :

[0384] This example shows how the combination of gelatin and dextrose with PAE as the crosslinker affects the mechanical strength of the composite bars as compared to only gelatin with PAE or dextrose with PAE. The preparation of the binder could be done via a two-step method or a one-pot method. There is no clear difference in the results between the two methods. Here the amount of PAE was set to be 10 wt.% of the sum of gelatine and dextrose binder component solids, the binder pH was set to be 7 and the curing condition was 200 °C for 1 h. Both methods are described below.

[0385] Two-step method:

[0386] Preparation of a 25 wt.% G-PAE (gelatine mixed with PAE) solution. Gelatine (35 g, 80-100 bloom CamGlue Moreu) was added to water (81.67 g) and stirred in a 50 °C water bath for 30 mins or until completely dissolved to obtain a 30 wt.% solution. Kymene GHP20 solution (17.5 g, 10 wt.% of gelatin binder component solid) was added to the gelatin solution and the mixture was stirred for a few minutes at 50 °C to mix well. The pH of this mixture was measured (~ 5). To the mixture, 1 mol / L NaOH solution was added slowly to reach the target pH 7. Afterwards, 4 wt.% silane solution (1.75 g, 0.2 wt.% of organic binder component solid) was added, and extra water was added to adjust to the target binder component solid content of 25 wt.%.

[0387] Preparation of a 25 wt.% D-PAE (dextrose mixed with PAE) solution. The dextrose used here can be either a dextrose syrup or dextrose monohydrate solid. Dextrose syrup (75 wt.%) was pre-melted in a 80 °C water bath before use. 20 g of the melted dextrose syrup or 16.5 g dextrose monohydrate was added to 30 g water to obtain a 30 wt.% dextrose solution. To this solution, Kymene GHP20 solution (7.5 g, 10 wt.% of dextrose binder component solid) was added at room temperature and mixed well. The pH of the mixture was measured (~2.8). To the mixture, 1 mol / L NaOH solution was added slowly to reach the target pH 7. Afterwards, 4 wt.% silane solution (0.75 g, 0.2 wt.% of organic binder component solid) was added, and extra water was added to adjust to the target binder component solid content to 25 wt.%.

[0388] Finally, D-PAE and G-PAE were mixed at different weight ratios. In this example, mixtures of D-PAE and G-PAE with a gelatine:dextrose: (G:D weight ratio of 100:0, 95:5, 90:10, 75:25, 65:35, 50:50, and 0:100 were prepared. After mixing, the samples were kept stirring at 50 °C for a few minutes to mix well prior to making the composite bars.

[0389] One-pot method:

[0390] Here we take the mixing ratio of G:D = 90:10 (D10-G90) as an example. Gelatin (12 g, 80-100 bloom CamGlue Moreu) was added to water (28 g) and stirred at 50 °C for half an hour or until completely dissolved to obtain a 30 wt.% solution. To this solution, 75% dextrose syrup (1.78 g, 11.11 wt.% of gelatin binder component solid) or dextrose monohydrate (1 .47 g, 11.11 wt.% of gelatin binder component solid) and Kymene GHP20 (6.67 g, 10 wt.% of organic binder component solid) was added, and the mixture was stirred 50 °C for a few minutes before adjusting the pH. 1 mol / L NaOH was added dropwise to increase the pH to 7. Afterwards, 4 wt.% silane solution (0.74 g, 0.2 wt.% of organic binder component solid) was added. Extra amount of water was added to reach a binder component solid content of 25 wt.%. After mixing, the samples was kept stirring at 50 °C for a few minutes to mix well prior to making the composite bars. Other mixing ratios used in the examples were done in the same way except by varying the amount of dextrose added to change the mixing ratio D: G. The detailed binder component solid contents of the different binders are shown in Table 3 and the results are shown in Figure 1.

[0391] Table 3. Detailed binder component solid content of the binders presented in

[0392] Example 1

[0393] Gelatine (%) 89.88 85.40 80.91 67.46 58.48 45.00 0.00

[0394] Dextrose (%) 0.00 4.50 8.99 22.49 31.49 45.00 90.16

[0395] PAE (%) 8.99 8.99 8.99 9.00 9.00 9.00 9.02

[0396] NaOH (%) 0.96 0.94 0.93 0.88 0.85 0.80 0.65

[0397] Silane (%) 0.18 0.18 0.18 0.18 0.18 0.18 0.18 a: D0-G100 means the weight ratio between gelatine and dextrose in the binder component solid is 100:0, D5-G95 means the weight ratio between gelatine and dextrose is 95:5, and so on.

[0398] The results are shown in Figure 1 which shows the mechanical strength of the composite bars presented in Example 1 and the corresponding binder solubility in water, prepared with different mixing ratios of dextrose and gelatin with 10 wt.% PAE as the crosslinker using one-pot method, with PUF as reference. From Figure 1 , it is evident that the combination of dextrose and gelatin with PAE as crosslinker showed improved mechanical properties, especially unaged strength, than only dextrose with PAE or only gelatin with PAE. Further, the combination of dextrose and gelatin with PAE as crosslinker showed improved strength properties that are comparable with the reference binder (PUF), thus proving the feasibility of this invention. The addition of saccharide also lowers the water solubility of the binder significantly compared to binders made with gelatin and PAE, which is another merit of adding dextrose to the binder composition, without being bound by theory we believe the reason for improved mechanical strength is that the aldehyde and hydroxyl groups on dextrose and other saccharides could also react with gelatin and with PAE during curing. Compared to a binder made with gelatine and PAE, the addition of saccharide - here dextrose - increases the crosslinking density in the three-dimensional polymeric structure, which results in better mechanical strength. Also, the binders made with dextrose, gelatin and PAE, especially binders with protein:saccharide ratios from 95:5 to 75.5: 24.5 (or 75:25) have comparable or even higher mechanical strength than the reference PUF binder. The examples show a clear synergy in the effect on mechanical strengths, binder solubility and biodegradation behavior between the gelatin and the saccharides in the binder compositions.

[0399] Example 2:

[0400] This example is to show if a lower amount of the crosslinker PAE could also be used without compromising the mechanical properties. This is mainly due to the consideration that PAE is an expensive chemical and reducing the amount of usage could result in a cost reduction. The binders were prepared in the same way as in the two-pot method in Example 1 , except that the PAE amount was lowered to 5 wt.% of the combined gelatin and dextrose binder component solids. The curing conditions were the same as in Example 1. The detailed binder component solid contents of the different binders are shown in Table 4 and the results are shown in Figure 2. Table 4. Detailed binder component solid content of the binders presented in

[0401] Example 2

[0402] Gelatine (%) 94.35 89.65 84.95 70.83 61.41 47.27 0.00

[0403] Dextrose (%) 0.00 4.72 9.44 23.61 33.07 47.27 94.72

[0404] PAE (%) 4.72 4.72 4.72 4.72 4.72 4.73 4.74

[0405] NaOH (%) 0.74 0.72 0.70 0.64 0.61 0.55 0.35

[0406] Silane (%) 0.19 0.19 0.19 0.19 0.19 0.19 0.19 a: D0-G100 means the weight ratio between gelatin and dextrose is 100:0, D5- G95 means the weight ratio between gelatin and dextrose is 95:5, and so on.

[0407] In figure 2, the mechanical strength of the composite bars presented in Example 2 and the corresponding binder solubility in water prepared with different ratios of the D-PAE and G-PAE with 10 wt.% PAE or 5 wt.% PAE, with PUF as reference. The 10 wt.% PAE data shown in fig. 2 were extracted from Example 1 for better comparison.

[0408] From Figure 2, it is seen that compared to 10 wt.% PAE, with only 5 wt.% PAE, the mechanical strength of the bars is clearly lower, especially the unaged strength. The water solubility is also higher with 5% PAE. Therefore, the amount of PAE in this binder system cannot be too low as it significantly affects the mechanical strength. Similar to Example 1 , at 5 wt.% PAE level, the combination of gelatin and dextrose with PAE as crosslinker showed much better mechanical strength and lower binder solubility than gelatin or dextrose alone with PAE, again confirming the positive effect of combining gelatin and dextrose. Although slightly lower, the mechanical strength, especially unaged mechanical strength, is comparable to the PUF reference binder, especially for D10-G90 and D25-G75, and also therebetween. Example 3:

[0409] This example is to show how different amounts of PAE and the curing temperature affects the mechanical strength.

[0410] Similar to Example 1 and 2, binders with 5 wt.%, 7.5 wt.% and 10 wt.% of PAE were prepared using the two-pot method. To ensure the sufficient high amount of gelatin binder component solid content (80%), the mixing ratios of D-PAE and G- PAE vary at each PAE level. The detailed binder component solids are shown in Table 5. Under each level of PAE, three different curing temperatures were tested: 175 °C, 200 °C, and 225 °C. The curing time was all fixed at 1 h. The detailed binder component solid contents of the different binders are shown in Table 5 and the results are shown below in Figure 3 to 5.

[0411] Table 5. Detailed binder component solid content of the binders presented in

[0412] Example 3

[0413] Dextrose : gelatine 15:85 13:87 10:90

[0414] Gelatine (%) 80.29 80.14 80.88

[0415] Dextrose (%) 14.17 11.98 8.99

[0416] PAE (%) 4.72 6.91 8.99

[0417] NaOH (%) 0.64 0.79 0.97

[0418] Silane (%) 0.19 0.19 0.19

[0419] Figure 3 shows the mechanical strength of the composite bars prepared with 5% PAE cured at three different temperatures and the corresponding binder solubility, with PUF as reference.

[0420] Figure 4 shows the mechanical strength of the composite bars prepared with 7.5% PAE cured at three different temperatures and the corresponding binder solubility, with PUF as reference. Figure 5 shows the mechanical strength of the composite bars prepared with 10% PAE cured at three different curing temperatures and the corresponding binder solubility, with PUF as reference.

[0421] From the above results, we see that the amount of PAE and the curing temperature have a clear impact on the mechanical strength of the composite bars. At high curing temperature (225 °C), the unaged strength gets significantly lower, while at curing temperatures of175 °C and 200 °C the unaged strength is comparable. The binder solubility increases with higher curing temperature, regardless of the PAE level. This is believed to be caused by the thermal degradation of gelatin at higher curing temperatures. This is confirmed further by the lower LOI when curing at 225 °C (2.35%), compared to LOI at the curing temperatures 200 °C (2.50%) and 175 °C (2,63%) In terms of the amount of PAE, 7.5 wt.% showed better overall mechanical strength than bars made with 5 wt.% or 10 wt.%. We assume that in this three-component binder system, the saccharide component (exemplified by dextrose) provides the cured binder with improved mechanical strength while PAE improves the crosslinking efficiency. With high amount of saccharide and low amount of PAE, the crosslinking density is low in the polymeric network while a high amount of saccharide provides higher mechanical strength. Vice versa, with low amount of saccharide and high amount of PAE, the crosslinking density is high but the high amount of PAE per se does not contribute to improve mechanical strength. Therefore, the mechanical strength of this binder is a result of the delicate balance between the ratio of dextrose and PAE. For the following experiments, 7.5 wt.% PAE and a curing temperature at 200 °C was chosen as the optimal condition.

[0422] Example 4:

[0423] This example is to show the pH effect on the mechanical strength of the binder. Next, the influence of reaction pH on the mechanical strength of the composite bars was studied. According to the PAE supplier (Solenis), PAE solution itself is acidic with a pH of 2 to 3, and it works the best in neutral to slightly alkaline pH. In practice, after mixing the three main ingredients (gelatine, dextrose, and PAE) in water at the described ratio, the pH of the mixture is ca. 5. Therefore, the optimal reaction pH was studied from 5 to 9. The binders were prepared in the same way as in Example 3 with 7.5 wt.% PAE but using one-pot method, and except the target pH was adjusted differently using NaOH to adjust pH. The detailed binder component solid contents of the binder at different pH are shown in Table 6 and the results are shown in Figure 6.

[0424] Table 6. Detailed binder component solids of the binders presented in Example

[0425] 4

[0426] Gelatine (%) 80.77 80.31 80.01 79.79 79.43

[0427] Dextrose (%) 12.07 12.00 11.96 11.92 11.87

[0428] PAE (%) 6.96 6.92 6.90 6.88 6.85

[0429] NaOH (%) 0.00 0.57 0.93 1.21 1.66

[0430] Silane (%) 0.20 0.20 0.20 0.20 0.20

[0431] Figure 6 shows the mechanical strength of the composite bars and the corresponding binder solubility of the binders in Example 4, with PUF as reference

[0432] In general, from the example 4 as shown in figure 6, the reaction pH does not have a significant influence neither on the mechanical strength nor the binder solubility. Only minor differences could be seen in the mechanical strength seen from pH 5 to pH 9. Thus, pH 6-8 was chosen as the pH for the following experiments.

[0433] Example 5:

[0434] This example shows the effect of different saccharides on the binder. How the choice of saccharide affects the mechanical strength of the binder was also investigated. Here we chose some reducing and non-reducing saccharides with different molecular sizes to show the influence of different saccharides. The list of saccharides tested in this example is shown in Table 7. Since all the monosaccharides are reducing sugars, and thus they are assumed to behave similarly. Therefore, only dextrose was tested in this category. The experimental procedures were similar to Example 4 but using the one pot method, except that the target pH was 6 and dextrose was replaced by the listed sugars below. The detailed binder component solid contents of the binders are shown in Table 8 and the results are shown in Figure 7.

[0435] Table 7. List of sugars tested in Example 5

[0436] Dextrose (DEX) Reducing 180.2 100 monosaccharide

[0437] Sucrose (SUC) Non-reducing 342.3 0 disaccharide

[0438] Maltose (MAL) Reducing 342.3 52 disaccharide

[0439] Lactose (LAC) Reducing 342.3 52 disaccharide

[0440] Raffinose (RAF) Non-reducing 504.4 0 trisaccharide

[0441] Melezitose (MEL) Non-reducing 504.4 0 trisaccharide

[0442] Maltotriose (MAT) Reducing 504.4 36 trisaccharide

[0443] Maltodextrin DE 4-7 (MAD 4-7) Reducing 2570-4500 4-7 oligosaccharide Maltodextrin DE 15-20 (MAD Reducing 900-1200 15-20

[0444] 15-20) oligosaccharide

[0445] Table 8. Detailed binder component solids of the binders presented in Example

[0446] 5

[0447] Gelatine (%) 79.91 79.88 79.89 79.90 79.88 79.88 79.86 79.89 79.89

[0448] Sugar (%) 11.94 11.94 11.94 11.94 11.94 11.94 11.93 11.94 11.94

[0449] PAE (%) 6.89 6.89 6.89 6.89 6.89 6.89 6.88 6.89 6.89

[0450] NaOH (%) 1.07 1.11 1.10 1.08 1.11 1.11 1.13 1.10 1.09

[0451] Silane (%) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20

[0452] Figure 7 shows the mechanical strength of the composite bars and the corresponding binder solubility of the binders in Example 5, with PUF as reference. DEX: dextrose, SUC: sucrose, MAL: maltose, LAC: lactose, RAF: raffinose, MEL: melezitose, MAT: maltotriose, MAD 4-7: maltodextrin with DE of 4-7, MAD 15-20: maltodextrin with DE of 15-20.

[0453] It was observed that all the reducing saccharides (dextrose, maltose, lactose, maltotriose, maltodextrin DE 4-7, and maltodextrin DE 15-20) showed a clearly better mechanical strength than the non-reducing saccharides (sucrose, raffinose, melezitose), especially in unaged strength. For high DE value saccharides (DE 100, 52, 36), no differences were observed, but for low DE value saccharides, namely, maltodextrin with DE 4-7 and maltodextrin with DE 15-20, the latter had a higher unaged strength than the former. The difference between reducing and non-reducing saccharide is most likely caused by the Maillard reaction between the nucleophiles on the gelatin (-OH, -NH2) and the aldehyde group (-CHO) in the reducing saccharide. This will increase the crosslinking density in the binder. Higher crosslinking density leads to a higher mechanical strength. When is DE is sufficiently high (36 and above), the nucleophiles on gelatin are fully reacted by the aldehyde groups, when the DE value is lower, there is not enough aldehyde that could react with all the nucleophiles, resulting in lower crosslinking density. Also, there is a good correlation between the mechanical strength and binder solubility: High mechanical strength comes with a low binder solubility, and vice versa. For further improving mechanical strength in this binder system, a reducing saccharide with a high DE value (36 and above) is preferred.

[0454] Example 6:

[0455] This example is to show whether different monosaccharides have an impact on the binder’s properties, especially mechanical strength.

[0456] To further confirm that a reducing saccharide is preferred in this binder system, we tested a range of different monosaccharides since all monosaccharides are reducing saccharides either by nature or via a tautomerisation step. Ketoses tautomerizes into an aldose, e.g. D-fructose, tautomerizes into D-glucose or D mannose). The composite bars were prepared in the same manner as in the previous Example 4 but using one pot method, except that the target pH was 6 and the different monosaccharides were used to replace dextrose. The monosaccharides tested in this example include dextrose (DEX), fructose (FRU), galactose (GAL), mannose (MAN), xylose (XYL), arabinose (ARA), rhamnose (RAH), and ribose (RIB). The detailed binder component solid contents of the binders are shown in Table 9 and the results are shown in Figure 8.

[0457] Table 9. Detailed binder component solids of the binders presented in Example

[0458] 6

[0459] Gelatine (%) 79.84 79.84 79.85 79.85 79.84 79.86 79.84 79.83

[0460] Sugar (%) 11.93 11.93 11.93 11.93 11.93 11.93 11.93 11.93

[0461] PAE (%) 6.88 6.88 6.88 6.88 6.88 6.89 6.88 6.88

[0462] NaOH (%) 1.15 1.15 1.13 1.13 1.15 1.12 1.15 0.16

[0463] Silane (%) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Figure 8 shows the mechanical strength of the composite bars and the corresponding water solubility of the binders in Example 6, with PUF as reference. Dex: dextrose, FRU: fructose, GAL: galactose, MAN: mannose, XYL: xylose, ARA: arabinose, RAH: rhamnose, RIB: ribose.

[0464] As expected, since all the monosaccharides are reducing sugars, there was no significant difference in the mechanical strength. As for binder solubility, only rhamnose showed slightly higher solubility. These results further confirms that a reducing saccharide is preferred in the present binder system.

[0465] Example 7:

[0466] This example shows the effect of different gelatines (mainly with different bloom values) on the binder properties.

[0467] Gelatine is the main component in this binder and its properties vary vastly depending on the source and / or Bloom value of the raw material, and whether (or how) it is subjected to hydrolysis, etc. In this example, we tested several different gelatins of different origin and gelatins with different Bloom values as well as a partially hydrolyzed gelatin to see if they have an impact on the mechanical strength of the binder. The binder was prepared in the same manner as in Example 4 using one pot method, except that the target pH was 6 and different gelatin samples were used instead of CamGlue 80-100 bloom gelatin. The detailed binder component solid contents are shown in Table 10 and the results are shown in Figure 9. Table 10. Detailed binder component solids of the binders presented in Example

[0468] 7

[0469] Protein (%) 79.53 79.89 80.01 79.90 79.86 79.61

[0470] Dextrose (%) 11.88 11.94 11.96 11.94 11.94 11.90

[0471] PAE (%) 6.86 6.89 6.90 6.89 6.89 6.86

[0472] NaOH (%) 1.54 1.09 0.94 1.07 1.12 1.44

[0473] Silane (%) 0.20 0.20 0.20 0.20 0.20 0.20

[0474] Figure 9 shows the mechanical strength of composite bars and the corresponding binder solubility of the binders presented in Example 8, with PUF as reference

[0475] The results showed that gelatin from different sources showed quite different strengths. Also gelatin from the same supplier but with different Bloom values, also has a clear impact on the mechanical strength. The optimal strength was observed with gelatines having a Bloom value of 0 to at least 180. For the stone wool production example further below, CamGlue 80-100 bloom gelatine was used.

[0476] Example 8:

[0477] This example is to show the effect of other non-collagen proteins on the binder In this example, some non-collagen proteins, including both plant based, and animal based, were tested to see the impact of protein types on the mechanical strength of the binder. The preparation of the binder was done in the same manner as the one-pot method and otherwise similar to Example 4, except that the target pH was 6 and gelatin was replaced by the proteins listed in table 11 below and the preparation of the binders were done at room temperature without heating. The detailed binder component solid contents of the binders are shown in Table 11 and the results are shown in Figure 10. Table 11. Detailed binder component solids of the binders shown in Example 8

[0478] Protein (%) 80.28 80.47 80.45 80.67 80.53 80.66 80.66 80.71

[0479] Dextrose (%) 12.00 12.03 12.03 12.05 12.03 12.05 12.05 12.06

[0480] PAE (%) 6.92 6.94 6.94 6.96 6.94 6.95 6.95 6.96

[0481] NaOH (%) 0.60 0.37 0.37 0.12 0.29 0.13 0.13 0.07

[0482] Silane (%) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20

[0483] Figure 10 shows the mechanical strength of composite bars and the corresponding binder solubility of the binders presented in Example 8, with PUF as a reference.

[0484] Compared to other non-collagen-based proteins, gelatine showed the best overall mechanical strength, especially in unaged strength, while whey protein isolate and egg albumin are also promising candidates with comparable aged strength and significantly lower binder solubility. Other tested proteins are considered as nonsuitable for this binder application.

[0485] Example 9:

[0486] This example is to show the possible alternatives to saccharides.

[0487] In this example, we were interested to see if saccharides could be replaced / substituted by non-saccharide alternatives. This is due to the consideration that since saccharides reacts with both gelatin and PAE in this binder system, alternative non-saccharide based substitutes might also work in this binder system. Several saccharide substitutes, which are known for their ability to crosslink with proteins were tested. The composite bars were prepared in the same manner as in Example 4 but using one pot method, and except that the target pH was 6 and isophthalaldehyde (IPA), glyoxal (GLY) or tannin (TAN) was used instead of dextrose. The detailed binder component solid contents of the binder are shown in Table 12 and the results are shown in Figure 11.

[0488] Table 12. Detailed binder component solids of the binders shown in Example 9

[0489] Gelatine (%) 80.26 80.23 79.65 80.77

[0490] Sugar or the substitute (%) 11.99 11.99 11.90 12.07

[0491] PAE (%) 6.92 6.92 6.87 6.96

[0492] NaOH (%) 0.63 0.67 1.38 0.00

[0493] Silane (%) 0.20 0.20 0.20 0.20

[0494] Figure 11 shows the mechanical strength of composite bars and the corresponding binder solubility of the binders presented in Example 9, with PUF as reference. IPA: isophthalaldehyde, GLY: glyoxal, TAN: tannin.

[0495] The results above show that besides sugar / dextrose, other saccharide substitutes, for example IPA, provide comparable mechanical strength to dextrose, while glyoxal and tannin are not working as well as dextrose. Glyoxal provides unaged mechanical strength that is comparable to the PUF reference while the aged strengths are significantly higher than the PUF reference binder.

[0496] Example 10:

[0497] This example is to show the effect of the concentration silane in the aqueous binder

[0498] This example illustrates how different amounts of silane affects the mechanical strength of the binder. The binders were prepared in the same manner as in example 4 but using one pot method, and except that the target pH was 6, and the silane binder component solid was varied from 0% to 1 .8%, instead of fixed at 0.2%. The detailed binder component solid contents of the binders are shown in Table 13 and the results are shown in Figure 12. Table 13. Detailed binder component solids of the binders shown in Example 10

[0499] Gelatine (%) 80.28 80.21 80.02 79.85 79.67 79.50

[0500] Dextrose (%) 12.00 11.99 11.96 11.93 11.90 11.88

[0501] PAE (%) 6.92 6.92 6.92 6.89 6.87 6.85

[0502] NaOH (%) 0.80 0.69 0.69 0.35 0.18 0.00

[0503] Silane (%) 0.00 0.20 0.60 0.99 1.38 1.77

[0504] Figure 12 shows the mechanical strength of composite bars and the corresponding binder solubility of the binders presented in Example 10, with PUF as reference.

[0505] The results indicated that silane plays important role in improving the mechanical strength even further, especially in aged strength. With only 0.2% silane, a significant increase in both autoclave aged and water bath aged strengths is already seen, compared to without any silane added. Further increasing of silane content to above 0.6% only resulted in small to negligible further increases in the mechanical strengths.

[0506] Example 11 :

[0507] This example is to show how the ratio between dextrose and gelatine affects the biodegradation kinetics.

[0508] This example illustrates the biodegradation behavior of the binders with different ratios of dextrose to gelatin. Biodegradation behavior is investigated under either aerobic biodegradation condition at room temperature or static controlled composting conditions at 58 °C. The binders were prepared in the same way as in Example 1 using the one-pot method, except that the target pH was 6, the PAE binder component solid content was 7.5 wt.% of gelatine and dextrose. The binders were cured at 200 °C for 1 h. The detailed binder component solid contents of each binder are listed in Table 14. The mechanical strength of the binders was also tested with the composite bars, as shown in Figure 13. The biodegradation results are shown in Figure 14-17.

[0509] Table 14. Detailed binder component solid contents of the binders investigated for biodegradation behavior in Example 11

[0510] Gelatin (%) 91.62 87.10 82.56 73.49 64.39 0.00

[0511] Dextrose (%) 0.00 4.58 9.17 18.37 27.59 91.62

[0512] PAE (%) 6.87 6.88 6.88 6.89 6.90 6.87

[0513] NaOH (%) 1.32 1.25 1.19 1.06 0.93 1.32

[0514] Silane (%) 0.20 0.20 0.20 0.20 0.20 0.20 a: D0-G100 indicates the binder component solid ratio between gelatin and dextrose is 100:0 (no dextrose), and D5-G95 indicates the binder component solid ratio between gelatin and dextrose is 95:5, and so on.

[0515] Figure 13 shows the mechanical strength of composite bars and the corresponding binder solubility of the binders presented in Example 11 , with PUF as reference.

[0516] Figure 14 shows the room temperature (25 °C) aerobic biodegradation test of the binders with different binder component solid ratios of gelatine and dextrose over a test period of 28 days (duplicate). D0-G100 indicates the binder component solid ratio between gelatin and dextrose is 100:0 (no dextrose), and D5-G95 indicates the binder component solid ratio between gelatin and dextrose is 95:5, and so on.

[0517] Figure 15 shows the aerobic biodegradation test under static controlled composting conditions (58°C) of binder D0-G100 (duplicate, RN3 and RN8) over a test period of 45 days. Biodegradation % on the Y axis in % is absolute, i.e. by weight, relative to the weight of the starting material). D0-G100 indicates the binder component solid ratio between gelatin and dextrose is 100:0, namely, no dextrose in this binder.

[0518] Figure 16 shows the aerobic biodegradation test under static controlled composting conditions (58°C) of binder D50-G50 (duplicate, RN4 and RN9) over a test period of 45 days. Biodegradation % on the Y axis in % is absolute, i.e. by weight, relative to the weight of the starting material). D50-G50 indicates the binder component solid ratio between gelatin and dextrose is 50:50.

[0519] Figure 17 shows the room temperature (25 °C) aerobic biodegradation of PUF binder (duplicate, RN3 and RN7) over a test period of 120 days. Biodegradation % on the Y axis in % is absolute, i.e. by weight, relative to the weight of the starting material).

[0520] From the figures above, it is seen that the incorporation of dextrose has a significant impact on the biodegradation kinetics of the binder. From the lab screening results (Figure 14), it is seen that the more dextrose added, the slower biodegradation becomes. The external results (Figure 15-16) further confirmed the result. Without any dextrose added in the binder (D0-G100), the binder reached an absolute biodegradation degree of over 80%, which indicates the excellent biodegradability of binders based on proteins, here illustrated with gelatin. While with the same amount of gelatin and dextrose in the binder (D50- G50), only less than 20% absolute biodegradation degree was reached within the same test period. Therefore, the biodegradation behavior of this binder is tunable by adjusting the amount of sugar added. Compared to PUF, this binder system has a much higher biodegradability, as PUF is non-biodegradable (Figure 17). To reach a biodegradable certification (90% biodegradation within the test period), the amount of gelatin in the binder should be sufficiently high enough as gelatin / protein is the main biodegradable component in this binder. Example 12:

[0521] This example is to show how different saccharides and saccharide alternatives affect the biodegradation kinetics of the binder.

[0522] This example illustrates the influence of different saccharides and saccharide alternatives on the biodegradation behavior of the binder. The binders were prepared in the same way as in Example 5 with the selected saccharides and saccharide alternatives using one pot method, and the results are shown in Figure 18 and 19.

[0523] Figure 18 shows the room temperature (25 °C) aerobic biodegradation test of the binders prepared with saccharides having different molecular sizes over a test period of 28 days. DEX: dextrose, SUC: sucrose, MAL: maltose, LAC: lactose, MEL: melezitose, MAT: maltotriose, MAD 4-7: maltodextrin DE 4-7, MAD 15-20: maltodextrin DE 15-20.

[0524] Figure 19 shows the room temperature (25 °C) aerobic biodegradation test of the binders prepared with different monosaccharide sugars and sugar alternatives over a test period of 28 days. DEX: dextrose, FRU: fructose, GAL: galactose, MAN: mannose, XYL: xylose, IPA: isophthalaldehyde, GLY: glyoxal.

[0525] Overall, the choice of saccharide or saccharide alternative has a clear impact on the biodegradation kinetic of the binder. Compared to binders without saccharide, adding one or more saccharides or saccharide alternatives all slows down the biodegradation. Among different saccharides, dextrose is the most effective one, which means, for the same amount of saccharide, a binder comprising dextrose always shows the slowest biodegradation. In terms of saccharide alternatives, the addition of glyoxal shows a significant decrease in biodegradation, which is even lower than dextrose. Example 13:

[0526] This example is to show the simulated emissions from production of mineral fibre products with a cured binder composition according to the present disclosure. Simulations of emissions from spinning chamber / formation chamber as well as from curing stage were made.

[0527] The binder compositions were prepared in the same way as in Example 8 with the dextrose, three selected proteins, namely, gelatine, whey protein isolate and egg albumin, and PAE as crosslinker as indicated in Table 15 using one pot method. The resulting simulated emission results are shown in Table 16, with PUF as a reference. Note that only analytes with an emission intensity higher than 1 milligram per gram binder solid in any of the binders were presented and highlighted in bold, as only above this intensity is considered as a significant emission.

[0528] Table 15. Detailed binder component solid contents of the three binders investigated for simulated emissions in Example 13:

[0529] Protein (%) 80.28 80.67 80.66

[0530] Dextrose (%) 12.00 12.05 12.05

[0531] PAE (%) 6.92 6.96 6.95

[0532] NaOH (%) 0.60 0.12 0.13

[0533] Silane (%) 0.20 0.20 0.20 Table 16. Detailed simulated emission of the three binders presented in Example 13:

[0534] Acetic acid 0.31 0.18 0.19 3.16 0.05 4.01 0.12 3.35

[0535] CO 0.02 0.10 0.01 0.01 0.01 1.69 0.03 2.13

[0536] CO2 1.84 27.61 0.94 20.03 1.30 20.66 0.81 9.46

[0537] Formaldehyde 1.54 0.28 0.00 0.06 0.00 0.03 0.00 0.04

[0538] HCNO 0.28 8.15 0.08 0.81 0.15 0.52 0.17 0.85

[0539] MeOH 7.30 0.02 0.01 0.02 0.01 0.01 0.01 0.01

[0540] NH321.85 28.03 0.30 2.98 0.04 3.08 0.03 2.98

[0541] Phenol 1.20 0.21 0.01 0.25 0.00 0.17 0.00 0.16

[0542] Urea 1.02 0.48 0.84 0.27 0.89 0.10 0.91 0.14

[0543] The results showed that, as compared to PUF reference, the three binders presented in this example showed significantly lower emissions. In simulated spinning chamber emissions, formaldehyde, methanol, ammonia, phenol and urea emissions were significantly reduced as compared to PUF. In simulated curing oven emissions, CO2, fulminic acid (HCNO) and ammonia emissions were also significantly lower as compared to PUF. The main noticeable increase in emission compared to PUF is acetic acid in the simulated curing oven emissions for all the 3 binders. Without being bound by theory it is believed that this is most likely due to the thermal decomposition of the proteins under high temperature curing. A slight increase in CO was also observed for whey protein isolate and egg albumin binders in curing oven simulated emissions. Overall, the binders have a much greener emissive profile as they exhibit very low levels of emissions.

[0544] Production example

[0545] Binder mixing

[0546] To a 1 m3IBC, 583 L hot water (80 °C) was added. The water was kept warm at 50 °C using a bottom heater. To the water, technical gelatine powder (230 kg, 80 bloom CamGlue Moreu) and dextrose monohydrate powder (38 kg) was added. The mixture was kept stirring until all the powder was dissolved and no large lumps were seen. This solution could be prepared well in advance before production. Just before using the aqueous binder composition in the production, 99 kg Kymene GHP20 PAE was pumped into the IBC, followed by 12 kg NaOH solution (25%, w.t.) and 1.4 kg silane solution (40%, w.t.). The resulting yellowish mixture was then used for production of stone wool.

[0547] Alternatively, the components could be mixed in an in-line fashion.

[0548] Binder and additive dosing

[0549] The above binder mixture was diluted as appropriate / required with process water (normally diluted to binder component solid of 10%) and dosed to the cascade spinner

[0550] Curing

[0551] The stone wool product was cured with air heated to a temperature of approx. 270 °C that resulted in a core temperature of the wool in the vicinity of 215-250 °C.

[0552] Test methods used in production examples were according to the following standards:

[0553] Ignition loss(%): EN 13820:2003

[0554] Density (kg / m3), EN ISO 29470:2020

[0555] Water uptake (kg / m2), EN 1609:2013

[0556] Delamination o: EN 1607:2013

[0557] Compression strength o10: EN ISO 29469:2022

[0558] Point Load at 5 mm def. (N): EN 12430:2013 General comments and discussion

[0559] General comments

[0560] The present binder system is a new (at least partly) biodegradable binder with no added formaldehyde (NAF). Three main criteria this binder must meet are: good mechanical strength, biodegradability, and low phytotoxicity. The present binder system contains three main components, protein (gelatin in particular), saccharide(s) and PAE. To ensure sufficient biodegradability, the ratio of protein, e.g. gelatin, must be sufficient high as it is the only biodegradable ingredient in this binder. Preferably, the protein content is over 75% by weight of binder component solids. The amount of saccharide and crosslinker have an influence on the mechanical strength of the binder as well as the biodegradation kinetics. Other additives in the binder composition may include: pH adjusting agent, e.g. NaOH - to adjust the pH of the binder to a level that ensures sufficient reactivity of the crosslinker, coupling agents, e.g. amino silane - to increase the adhesion between the binder and the wool.

[0561] The unique crosslinking reactivity of PAE towards both proteins and carbohydrates is central to the present binder technology. In brief, the electrophilic four membered azetidinium rings in the PAE resin can both self-crosslink and cocrosslink with the carbohydrates and proteins to generate covalent bonds. This occurs by nucleophilic attack on the a-position of the azetidinium ring of a nucleophile from the carbohydrate or protein leading to ring opening and formation of a covalent bond.

[0562] The present binder system comprises no toxic components and is thus not only formaldehyde free, but also ammonia free. The curing emissions of the present binder system are the lowest of any of the current NAF-binder alternatives. Furthermore, the low emissions present in the present binder system can be handled by existing abatement systems. The following items relates to embodiments and preferred embodiments of the invention.

[0563] Item 1 . A mineral fibre aqueous binder composition, which aqueous binder composition comprises a) one or more protein(s) of non-plant origin, b) one or more saccharide(s) selected from monosaccharides, disaccharides, or oligosaccharides, or combinations or mixtures of two or more thereof; and c) a crosslinker comprising two or more azetidinium functional groups, and wherein the weight ratio of protein(s) to saccharide(s) (P:S) in binder component solids is between 75.5:24.5 and 99:1 .

[0564] Item 2. The aqueous binder composition according to item 1 , wherein the one or more protein(s) are selected from

[0565] - collagen or collagen derivatives, such as of animal origin, microbial origin and / or obtainable by use of recombinant technology, such as gelatine, such as partly hydrolysed gelatine; such as collagen type protein(s) of bovine, porcine, marine or recombinant origin;

[0566] - animal based proteins other than collagen type proteins, such as proteins from milk (casein, whey); proteins from eggs, such as albumin; proteins from marine animal sources; proteins from jellyfish; proteins from insects, such as silkworms, such as sericin;

[0567] - proteins originating from microorganisms, such as by means of recombinant techniques, such as natural and / or genetically modified proteins from fungi, algae, such as microalgae, or bacteria, in particular yeasts, such as yeast protein, yeast extract and / or undenatured or hydrolyzed or at least partly denatured mycoprotein; or mixtures of two or more thereof. Item 3. The aqueous binder composition according to item 1 or 2, wherein the at least one protein is selected from collagen or collagen derivatives, such as gelatine, such as partly hydrolysed gelatine, technical grade gelatine, such as bone glue, jelly glue, animal glue or food grade gelatines; such as collagen or gelatine of bovine or porcine origin or marine origin.

[0568] Item 4. The aqueous binder composition according to any of items 1 to 3, wherein the one or more proteins comprises collagen type proteins or partly hydrolysed collagen type proteins, such as gelatin or partly hydrolysed gelatin, and where said protein(s) have an average molecular weight of 1 - 100 kDa, such as 1.5 - 50 kDa, or preferably 2-30 kDa or preferably 1 -30 kDa.

[0569] Item 5a. The aqueous binder composition according to any of items 1 to 4, wherein the one or more saccharide(s) are selected from

[0570] - monosaccharides, such as dextrose (glucose), xylose, fructose, ribose, arabinose, lyxose, allose, altrose, mannose, gulose, iodose, galactose and / or talose;

[0571] - disaccharides, such as sucrose, lactose, maltose, trehalose and / or cellubiose;

[0572] - oligosaccharides, such as trisaccharides, such as melezitose, raffinose, maltotriose; tetrasaccharides, pentasaccharides or hexasaccharides, such as maltodextrins, in particular low molecular mass maltodextrins;

[0573] - glucose syrup and / or mixtures of two or more thereof.

[0574] Item 6. The aqueous binder composition according to any of items 1 to 4, wherein the one or more saccharide(s) is a reducing sugar selected from - monosaccharides, such as dextrose (glucose), xylose, fructose, ribose, arabinose, lyxose, allose, altrose, mannose, gulose, iodose, galactose and / or talose;

[0575] - disaccharides, such as, lactose, maltose, and / or cellobiose;

[0576] - oligosaccharides, such as trisaccharides, such as, maltotriose; tetrasaccharides, pentasaccharides or hexasaccharides, such as maltodextrins, in particular low molecular mass maltodextrins;

[0577] - glucose syrup and / or mixtures of two or more thereof.

[0578] Item 7. The aqueous binder composition according to any of the preceding items, wherein the one or more saccharide(s) have a molecular mass of 0.15 -4.0 kDa, 0.15 -3.5 kDa, such as 0.15 -1 .5 kDa, such as 0.15 -1 .2 kDa.

[0579] Item 8. The aqueous binder composition according to any of the preceding items, wherein the one or more saccharide(s) are selected from reducing saccharides.

[0580] Item 9. The aqueous binder composition according to any of the preceding items, wherein the one or more saccharide(s) are selected from a saccharide having a dextrose equivalent (DE) of 0 to 100.

[0581] Item 10. The aqueous binder composition according to any preceding items, wherein the one or more saccharide(s) is dextrose or a source comprising dextrose, such as glucose syrup, said dextrose source having a DE of 15 to 100, in particular of 25 to 100, more particular 30 to 100 or such as 35 to 100.

[0582] Item 11 . The aqueous binder composition according to any of the preceding items, wherein the one or more saccharide(s) is a glucose syrup having a DE of 85 to less than 100. Item 12. The aqueous binder composition according to any of the preceding items, wherein the one or more saccharides is a is a hexose, such as fructose, galactose, and / or mannose; and / or a pentose such as xylose, arabinose, rhamnose and / or ribose; and / or mixtures thereof.

[0583] Item 13. The aqueous binder composition according to any of the preceding items, wherein the weight ratio of protein to saccharide (P:S) is between between 99:1 and 80:20 or such as between 95:5 and80:20 more preferred between 90:10 and 80:20.

[0584] Item 14. The aqueous binder composition according to any of the preceding items, wherein the protein content in the binder composition is 69.5-91 .4 % by weight of binder component solids, or preferably 73.8-91 .4% by weight of binder component solids, such as 73.8-87.7 % by weight of binder component solids or more preferred 73.8-83.1 % by weight of binder component solids.

[0585] Item 15. The aqueous binder composition according to any of the preceding items, wherein the saccharide content in the binder composition is in the range of 0.9-22.6% by weight of binder component solids, such as 0.9-18.5 % by weight of binder component solids, or preferably 4.6-18.5 % by weight of binder component solids or more preferred 9.23-18.5% by weight of binder component solids.

[0586] Item 16. The aqueous binder composition according to any of the preceding items, wherein the crosslinker comprising two or more azetidinium functional groups is a polymer comprising two or more azetidinium functional groups, such as a homopolymer or a copolymer, said polymer preferably comprising one, two or more non-azetidinium monomer units incorporated into the polymer structure. Item 17. The aqueous binder composition according to any of the preceding items, wherein the crosslinker is a thermosetting crosslinking polymer comprising two or more azetidinium functional groups; and / or wherein the crosslinker is preferably a polyamidoepihalohydrin polymer or a polyaminoamidoepihalohydrin polymer or a polyamidoamineepihalohydrin polymer.

[0587] Item 18. The aqueous binder composition according to any of the preceding items, wherein the crosslinker is obtainable by reacting polyamidoamine resin with a halohydrin, preferably epichlorohydrin and / or epibromohydrin, and / or wherein the polyamidoamine resin is obtainable by reacting a polyamine and a polycarboxylic acid, and / or wherein the polyazetidinium polymer is the reaction product of epichlorohydrin or epibromohydrin, or a mixture thereof, and a polyamidoamine, which polyamidoamine is obtainable by reacting a diamine or a triamine, such as diethylenetriamine, or a mixture thereof, with the polycarboxylic acid, such as succinic acid, adipic acid, oxalic acid, phthalic acid, or a mixture of two or more thereof.

[0588] Item 19. The aqueous binder composition according to any of the preceding items, wherein said binder comprises the azetidinium functional crosslinker in an amount of 1 -20% by weight of binder component solids, such as 1 .5- 18 % by weight of binder component solids or preferably 2-16 % by weight of binder component solids or preferably 5-15% by weight of binder component solids.

[0589] Item 20. The aqueous binder composition according to any of the preceding items, wherein the binder composition does not comprise a protein from vegetable source(s) such as soybeans (soy protein). Item 21. The aqueous binder composition according to any of the preceding items,

[0590] A: wherein the protein content in the binder composition is 69.5-91 .4 % by weight of binder component solids and the saccharide content in the binder composition is in the range of 0.9-22.6 % by weight of binder component solids and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18 % by weight of binder component solids or preferably 2-16 % by weight of binder component solids or preferably 5-15% by weight of binder component solids; or

[0591] B: wherein the protein content in the binder composition is 73.8-91.4% by weight of binder component solids, and saccharide content in the binder composition is in the range of 0.9-18.5% by weight of binder component solids and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18 % by weight of binder component solids or preferably 2-16 % by weight of binder component solids or preferably 5-15% by weight of binder component solids; or

[0592] C: wherein the protein content in the binder composition is 73.8-87.7% by weight of binder component solids and the saccharide content in the binder composition is in the range of 4.6-18.5% by weight of binder component solids and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18 % by weight of binder component solids or preferably 5-15% by weight of binder component solids or preferably 2-9% by weight of binder component solids; or

[0593] D: wherein the protein content in the binder composition is 73.8-83.1 % by weight of binder component solids and the saccharide content in the binder composition is in the range of 9.2-18.5 % by weight of binder component solids, and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18 % by weight of binder component solids or preferably 2-16 % by weight of binder component solids or preferably 5-15% by weight of binder component solids. Item 22. The aqueous binder composition according to any one of the preceding items, wherein the binder composition further comprises one or more additives selected from a group of one or more pH adjusters, such as one or more bases and / or one or more acids; one or more hardener(s), coupling agent(s) and / or adhesion promoter(s), such as a silane; one or more hydrophobic agents such as a silicone oil or silicone resin and / or fatty acid ester(s) of glycerol, one or more hydrophilic agents, one or more dust binding agent(s), such as oil(s), such as mineral oil(s) and / or one or more colouring agents.

[0594] Item 23. The aqueous binder composition according to any of the preceding items, wherein the binder composition further comprises at least one mineral oil and / or one or more fatty acid ester of glycerol, wherein the oil content is preferably 0.6 to 30, preferably 1 to 10, more preferably 2 to 7.5 % by weight, based on the binder component solids.

[0595] Item 24. The aqueous binder composition according to item 23 wherein the at least one fatty acid ester of glycerol is selected from one or more components from the group consisting of linseed oil, coconut oil, com oil, canola oil, cottonseed oil, olive oil, palm oil, peanut oil (ground nut oil), rapeseed oil, including canola oil, safflower oil, sesame oil, soybean oil, sunflower oil or combinations thereof.

[0596] Item 25. The aqueous binder composition according to any of the preceding items, further comprising a coupling agent, such as a silane, such as an amino silane, such as in an amount of 0.05-1.8 % by weight of binder component solids, preferably 0.1 -1.0 % by weight of binder component solids or more preferred 0.1 -0.6% % by weight of binder component solids.

[0597] Item 25a. The aqueous binder composition according to any of the preceding items, wherein said binder after curing is at least partly biodegradable

[0598] Item 26. A method of producing a bonded mineral fibre product which comprises the steps of contacting the mineral fibres with an aqueous binder composition according to any of the items 1 to 25 and curing the binder to form a cured mineral fibre product comprising a biodegradable binder.

[0599] Item 27. The method of producing a bonded mineral fibre product according to item 26 wherein the method comprises the steps of:

[0600] - making a melt of raw materials,

[0601] - fiberizing the melt by means of a fibre forming apparatus to form mineral fibres, wherein the mineral fibres formed are preferably directed into a spinning chamber,

[0602] - providing the mineral fibres in the form of a collected web,

[0603] - applying the aqueous binder composition on the mineral fibres before, during or after the provision of the collected web to form a mixture of mineral fibres and binder composition, wherein the aqueous binder composition is preferably applied by spraying before the provision of the collected web, preferably in the spinning chamber

[0604] - curing the binder composition mixed with the mineral fibres.

[0605] Item 28. The method of producing a mineral fibre product according to items 26 or 27, wherein the curing is carried out at temperatures from 180-280 °C, preferably 200-270 °C, more preferably 220-265 °C. Item 29. A mineral fibre product comprising mineral fibres bound by a biodegradable binder resulting from the curing of an aqueous binder composition according to any of the items 1 to 25.

[0606] Item 30. A mineral fibre product comprising mineral fibres bound by a biodegradable binder resulting from the curing of an aqueous binder composition according to the method of any of the items 26-28.

[0607] Item 31. A mineral fibre product according to item 29 or 30, wherein the density is in the range of 10-1200 kg / m3, such as 20-800 kg / m3, such as 10-600 kg / m3, or 30-600 kg / m3, such as 40-400 kg / m3, such as 50-250 kg / m3, such as 10-200 kg / m3or such as 40-200 kg / m3.

[0608] Item 32. A mineral fibre product according to any of the items 29-31 , wherein said cured mineral fibre product has an average density of 75-85 kg / m3and one or more of:

[0609] - a compression strength, such as unaged compression strength, at 10% o10 (kPa) according to EN ISO 29469:2022 -greater than or equal to 15 kPa, such as greater than or equal to 19 kPa and / or

[0610] - a delamination strength, such as unaged delamination strength, omt greater than or equal to 7.5 kPa, such as greater than or equal to 10 kPa, according to EN 1607.

[0611] Item 33. A mineral fibre product according to any of items 29-32, wherein the product is a mineral wool insulation product, such as a mineral wool thermal insulation product or a mineral wool acoustical insulation product.

[0612] Item 34. A mineral fibre product according to any of items 29 to 33, wherein the product is a granulate or a shaped product, such as a slab, a pad or a blanket, a rolled-up blanket or a shaped item, such as a tubular segment. Item 35. A mineral fibre product obtainable by a method according to any one of items 26 to 28.

[0613] Item 36. Use of an aqueous binder composition according to any of the items 1 to 25 for the production of a mineral fibre product bound by a cured biodegradable binder.

[0614] Item 37. Use of an aqueous binder composition according to any of the items 1 -25 for lowering of emissions, such as formaldehyde and / or ammonia and / or phenol emissions during production of a mineral fibre product.

[0615] Item 38. Use of an aqueous binder composition according to any of the items 1 -24 for production of formaldehyde free mineral fibre products where the emission is below 5 pg / m2 / h of formaldehyde from the mineral fibre product, preferably below 3 pg / m2 / h, when measured in accordance with ISO 16000 -1 :2004.

[0616] Item 39. A method for disposing of a mineral fibre product comprising mineral fibres bound by a biodegradable binder resulting from the curing of an aqueous binder composition according to any of the items 1 to 25, comprising the steps of

[0617] - optionally disintegrating the mineral fibre product, followed by

[0618] - subjecting the mineral fibre product to a composting step in which the biodegradable binder is decomposed by (micro)biological activity.

[0619] Item 40. A method according to item 38, wherein the composting step is performed under aerobic conditions.

[0620] Item 41 . Use of an inventive aqueous binder composition according to any of the items 1 -25 for production of a mineral fibre products where the MMVF binder is biodegradable after curing, such as able to be decomposed at least 20% (by weight of the starting material) within a period of 45 days when composted under aerobic conditions at 58°C according to ISO 14855-1 (2012).

Claims

Claims1. A mineral fibre aqueous binder composition, which aqueous binder composition comprises a) one or more protein(s) of non-plant origin, b) one or more saccharide(s) selected from monosaccharides, disaccharides, or oligosaccharides, or combinations or mixtures of two or more thereof; and c) a crosslinker comprising two or more azetidinium functional groups, and wherein the weight ratio of protein(s) to saccharide(s) (P:S) is between 75.5:24.5 and 99:1.

2. The aqueous binder composition according to claim 1 , wherein the one or more protein(s) of non-plant origin are selected from- collagen or collagen derivatives, such as of animal origin, microbial origin and / or obtainable by use of recombinant technology, such as gelatine, such as partly hydrolysed gelatine; such as collagen type protein(s) of bovine, porcine, marine, and / or recombinant origin;- animal based proteins other than collagen type proteins, such as proteins from milk (casein, whey); proteins from eggs, such as albumin; proteins from marine animal sources; proteins from jellyfish; proteins from insects, such as silkworms, such as sericin;- proteins originating from microorganisms, such as by means of recombinant techniques, such as natural and / or genetically modified proteins from fungi, algae, such as microalgae, or bacteria, in particular yeasts, such as yeast protein, yeast extract and / or undenatured or hydrolyzed or at least partly denatured mycoprotein; or mixtures of two or more thereof.

3. The aqueous binder composition according to claim 1 or 2, wherein the at least one protein is selected from collagen or collagen derivatives, such as gelatine, such as partly hydrolysed gelatine, technical grade gelatine, suchas bone glue, jelly glue, animal glue or food grade gelatines; such as collagen or gelatine of bovine or porcine origin or marine origin.

4. The aqueous binder composition according to any of claims 1 to 3, wherein the one or more proteins comprises collagen type proteins or partly hydrolysed collagen type proteins, such as gelatine or partly hydrolysed gelatine, and where said protein(s) have an average molecular weight of 1 -100 kDa, such as 1.5 - 50 kDa, or preferably 2-30 kDa or preferably 1 - 30 kDa.

5. The aqueous binder composition according to any of claims 1 to 4, wherein the one or more saccharide(s) are selected from- monosaccharides, such as dextrose (glucose), xylose, fructose, ribose, arabinose, lyxose, allose, altrose, mannose, gulose, iodose, galactose and / or talose;- disaccharides, such as sucrose, lactose, maltose, trehalose and / or cellubiose;- oligosaccharides, such as trisaccharides, such as melezitose, raffinose, maltotriose; tetrasaccharides, pentasaccharides or hexasaccharides, such as maltodextrins, in particular low molecular mass maltodextrins;- glucose syrup and / or mixtures of two or more thereof.

6. The aqueous binder composition according to any of claims 1 to 4, wherein the one or more saccharide(s) is a reducing sugar selected from- monosaccharides, such as glucose, such as dextrose, xylose, fructose, ribose, arabinose, lyxose, allose, altrose, mannose, gulose, iodose, galactose and / or talose;- disaccharides, such as lactose, maltose, and / or cellobiose;- oligosaccharides, such as trisaccharides, such as, maltotriose; tetrasaccharides, pentasaccharides or hexasaccharides, such as maltodextrins, in particular low molecular mass maltodextrins;- glucose syrup and / or mixtures of two or more thereof.

7. The aqueous binder composition according to any of the preceding claims, wherein the one or more saccharide(s) have a molecular mass of 0.15- 4.0 kDa, such as 0.15 -3.5 kDa, such as 0.15 -1 .5 kDa, such as 0.15-1 .2 kDa.

8. The aqueous binder composition according to any preceding claims, wherein the one or more saccharide(s) is dextrose or a source comprising dextrose, such as glucose syrup, said dextrose source having a DE of 15 to 100, in particular of 25 to 100, more particular 30 to than 100 or such as 35 to 100.

9. The aqueous binder composition according to any of the preceding claims, wherein the one or more saccharides is a hexose, such as a glucose, such as dextrose, such as a fructose, such as a galactose, and / or a mannose; and / or a pentose such as a xylose, an arabinose, rhamnose and / or ribose; and / or mixtures thereof.

10. The aqueous binder composition according to any of the preceding claims, wherein the weight ratio of protein to saccharide (P:S) is between 99:1 and 80:20 or such as between 95:5 and 80:20 more preferred between 90:10 and 80:20.11 . The aqueous binder composition according to any of the preceding claims, wherein the protein content in the binder composition is 69.5-91.4% by weight of binder component solids, or preferably 73.8-91.4% by weight of binder component solids, such as 73.8-87.7% by weight of bindercomponent solids or more preferred 73.8-83.1 % by weight of binder component solids.

12. The aqueous binder composition according to any of the preceding claims, wherein the saccharide content in the binder composition is in the range of 0.9-22.6% by weight of binder component solids, such as 0.9-18.5 % by weight of binder component solids, or preferably 4.6-18.5 % by weight of binder component solids or more preferred 9.23-18.5% by weight of binder component solids.

13. The aqueous binder composition according to any of the preceding claims, wherein the crosslinker comprising two or more azetidinium functional groups is a polymer comprising two or more azetidinium functional groups, such as a homopolymer or a copolymer, said polymer preferably comprising one, two or more non-azetidinium monomer units incorporated into the polymer structure.

14. The aqueous binder composition according to any of the preceding claims, wherein said binder comprises the azetidinium functional crosslinker in an amount of 1 -20% by weight of binder component solids, such as 1 .5-18 % by weight of binder component solids or preferably 2-16 % by weight of binder component solids or preferably 5-15% by weight of binder component solids.

15. The aqueous binder composition according to any of the preceding claims, A: wherein the protein content in the binder composition is 69.5-91.4% by weight of binder component solids and the saccharide content in the binder composition is in the range of 0.9-22.6% by weight of binder component solids and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18% by weight of bindercomponent solids or preferably 2-16% by weight of binder component solids or preferably 5-15% by weight of binder component solids; orB: wherein the protein content in the binder composition is 73.8-91.4% by weight of binder component solids, and saccharide content in the binder composition is in the range of 0.9-18.5% by weight of binder component solids and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18% by weight of binder component solids or preferably 2-16% by weight of binder component solids or preferably 5-15% by weight of binder component solids; orC: wherein the protein content in the binder composition is 73.8-87.7% by weight of binder component solids and the saccharide content in the binder composition is in the range of 4.6-18.5% by weight of binder component solids and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18 % by weight of binder component solids or preferably 5-15% by weight of binder component solids or preferably 2-9% by weight of binder component solids; orD: wherein the protein content in the binder composition is 73.8-83.1 % by weight of binder component solids and the saccharide content in the binder composition is in the range of 9.2-18.5 % by weight of binder component solids, and wherein the crosslinker is present in an amount of 1 -20% by weight of binder component solids such as 1.5-18 % by weight of binder component solids or preferably 2-16 % by weight of binder component solids or preferably 5-15% by weight of binder component solids.

16. The aqueous binder composition according to any of the preceding claims, further comprising a coupling agent, such as a silane, such as an amino silane, such as in an amount of 0.05-1 .8% by weight of binder component solids, preferably 0.1 -1.0% by weight of binder component solids or more preferred 0.1 -0.6% by weight of binder component solids.

17. The aqueous binder composition according to any of the preceding claims,wherein said binder after curing is at least partly biodegradable.

18. A method of producing a bonded mineral fibre product which comprises the steps of contacting the mineral fibres with an aqueous binder composition according to any of the claims 1 to 17 and curing the binder to form a cured mineral fibre product comprising a biodegradable binder.

19. The method of producing a mineral fibre product according to claim 18, wherein the curing is carried out at temperatures from 180-280 °C, preferably 200-270 °C, more preferably 220-265 °C.

20. A mineral fibre product comprising mineral fibres bound by a biodegradable binder resulting from the curing of an aqueous binder composition according to any of the claims 1 to 17.21 . Use of an aqueous binder composition according to any of the claims 1 -17 for lowering of emissions, such as formaldehyde and / or ammonia and / or phenol emissions during production of a mineral fibre product.

22. Use of an aqueous binder composition according to any of the claims 1 -17 for production of formaldehyde free mineral fibre products where the emission is below 5 pg / m2 / h of formaldehyde from the mineral fibre product, preferably below 3 pg / m2 / h, when measured in accordance with ISO 16000 -1 :2004.

23. A method for disposing of a mineral fibre product comprising mineral fibres bound by a biodegradable binder resulting from the curing of an aqueous binder composition according to any of the claims 1 to 17, comprising the steps of- optionally disintegrating the mineral fibre product, followed by- subjecting the mineral fibre product to a composting step in which the biodegradable binder is decomposed by (micro)biological activity.

24. A method according to claim 23 wherein the composting step is performed under aerobic conditions.

25. Use of an aqueous binder composition according to any of the claims 1 -17 for production of a mineral fibre product where the binder is at least partly biodegradable after curing, such as able to be decomposed at least 20% (by weight of the starting material) within a period of 45 days when composted under aerobic conditions at 58°C according to ISO 14855-1 (2012).

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