Mineral wool binder based on phenolic resin and protein

Abstract

The present invention relates to an aqueous binder composition made from a mixture of i) a phenol-urea-formaldehyde binder (PUF binder), and ii) a protein binder comprising at least one protein, and iii) at least one crosslinking agent selected from phenol-containing compounds. The aqueous binder composition is suitable for producing a mineral fiber product by contacting mineral fibers with the aqueous binder composition and curing the binder.

Description

Field of the Invention

[0001] The present invention relates to an aqueous binder composition comprising a mixture of a phenol-urea-formaldehyde binder and a protein binder, a method for producing a mineral wool product using the aqueous binder composition, and a mineral wool product produced by the method. Background of the Invention

[0003] Mineral wool products typically include man-made glass fibers (MMVF), such as glass fibers, ceramic fibers, basalt fibers, slag wool, mineral wool, and rock wool, which are bonded together by a cured thermosetting polymer binder. For use as thermal or acoustic insulation products, bonded mineral fiber mats are typically produced by converting a melt made from suitable raw materials into fibers in a conventional manner, such as by a spinning cup process or by a cascade rotor process. The fibers are blown into a forming chamber or spinning chamber, sprayed with a binder solution while still hot in air, and randomly deposited in the form of a mat or web on a traveling conveyor belt. The fiber mat is then transferred to a curing oven where hot air is blown through the fiber mat to cure the binder and firmly bond the mineral fibers together.

[0004] Phenolic binders, particularly phenol-formaldehyde resole resins, are frequently used in the manufacture of mineral fiber insulation materials such as insulative batts for use in walls, roof panels, ceilings, insulating coverings for pipes, and the like.

[0005] Typically, when phenolic resol resins are used as adhesives, large amounts of formaldehyde are emitted into the environment during processing, particularly during the curing process. Formaldehyde may also subsequently be released from the cured resin. Such formaldehyde emissions are undesirable, particularly in enclosed spaces, as they are harmful to human health and the environment. Formaldehyde has been classified as a human carcinogen by the International Agency for Research on Cancer (IARC) of the World Health Organization (WHO); see the iARC Monograph on Formaldehyde, Vol. 88 (2006). Therefore, it would be desirable to reduce formaldehyde emissions into the environment.

[0006] Various technologies have been used to reduce the release of formaldehyde from formaldehyde-based resins. In particular, various formaldehyde scavengers have been used for this purpose. For example, urea acts as a formaldehyde scavenger during and after the manufacture of bonded mineral fiber products. Urea is usually added directly to phenolic resins to produce urea-modified phenolic resols (also known as phenol-urea-formaldehyde resole resins). In order to obtain typical urea-modified resol adhesives, a mixture of phenol and formaldehyde is reacted with a suitable alkaline catalyst in one or more steps. Reaction conditions, temperature, the amount of catalyst, etc. are adjusted to favor phenol methylolation rather than condensation reaction. Urea is then added before or after the resin is deactivated when the resin is about to be used. This resin is commonly referred to as PUF resin or PUF adhesive.

[0007] Another commonly used formaldehyde scavenger is ammonia, which combines with formaldehyde to form amine compounds, such as hexamethylenetetramine.

[0008] For example, WO 96 / 26164 describes phenolic resin compositions for use as binders in mineral wool products, wherein phenol emissions are reduced by using a stoichiometric excess of formaldehyde over phenol, wherein excess formaldehyde emissions are reduced by adding ammonia as a formaldehyde scavenger, and wherein ammonia emissions are reduced by reacting ammonia with sugar compounds.

[0009] Other thermosetting phenolic resol-based mineral wool binder systems containing a sugar component are known in the art. For example, WO 2006 / 136614 discloses a binder system similar to that of WO 96 / 26164, but using hydroxylamine or amino alcohol instead of ammonia. US-A-4339361 discloses a phenolic resol resin suitable for use in a binder system for bonding mineral fiber products, the resin being extended with an amide or amine, such as urea, and a sugar as an inexpensive extender. The sugar component may be selected from monosaccharides and oligosaccharides, as well as water-soluble polysaccharides.

[0010] Another issue with previously known aqueous binder compositions for mineral fibers is that at least a large portion of the raw materials used to produce these binders are derived from fossil fuels. Consumers are increasingly preferring products produced entirely or at least partially from renewable materials, and there is a need to provide mineral wool binders that are produced at least partially from renewable materials. In this regard, binders based, in particular, on proteins or sugars have been developed.

[0011] WO 2017 / 194722 describes formaldehyde-free binder compositions for mineral fibers, comprising at least one phenolic and / or quinone-containing compound and at least one protein.

[0012] WO 2017 / 194721 relates to a mineral wool product comprising mineral fibers bonded by a cured binder, wherein the binder in its uncured state comprises at least one protein and at least one enzyme.

[0013] Such adhesives based on renewable resources, such as proteins, exhibit good performance. However, they also have some disadvantages compared to conventional phenolic resin adhesives. For example, protein-based adhesives can exhibit high solubility and high water absorption in their cured state, which are undesirable properties that compromise their use in certain applications.

[0014] As mentioned above, modifying phenol-urea-formaldehyde adhesives with ammonia as a formaldehyde scavenger is a known method for reducing formaldehyde emissions during adhesive use. On the other hand, modification with ammonia increases ammonia emissions from these systems. This is a particular problem when such adhesives are applied to mineral fibers in a spinning chamber. As mentioned above, the produced mineral fibers are blown into such a spinning chamber while still hot. Under these conditions, volatiles present in the uncured adhesive will evaporate during application. Consequently, when such adhesives are applied to mineral fibers in a spinning chamber, relatively high ammonia emissions result, which is highly undesirable.

[0015] Therefore, there remains a need to provide aqueous binder compositions based on phenolic binders suitable for bonding mineral fibers to produce mineral fiber products, wherein the binder compositions generate only low levels of harmful gases during processing. In particular, ammonia emissions are reduced, while formaldehyde emissions are also kept low. Furthermore, the mineral fiber products obtained by applying the binder to the mineral fibers and curing the binder should have very good mechanical properties and desirably low water absorption and solubility. SUMMARY OF THE INVENTION

[0017] It is therefore an object of the present invention to provide an aqueous binder composition which overcomes or mitigates the disadvantages of the prior art described above. In particular, it is an object of the present invention to provide a phenol-urea-formaldehyde based binder for mineral fibers which has reduced ammonia emissions during the processing of the binder while formaldehyde emissions remain low, in particular during application of the binder to the mineral fibers in a spinning chamber where the fiber temperature remains elevated.

[0018] At the same time, the adhesive in the cured state should exhibit satisfactory properties in terms of mechanical strength, solubility and water absorption.

[0019] The inventors have surprisingly found that this object can be solved by providing an adhesive composition made from a mixture of a phenol-urea-formaldehyde type adhesive (PUF adhesive) and a specific protein adhesive, even though these adhesive systems are generally considered to be incompatible with each other.

[0020] Therefore, the present invention relates to an aqueous adhesive composition made from a mixture of:

[0021] i) a phenol-urea-formaldehyde binder (PUF binder), and

[0022] ii) a protein binder comprising at least one protein and at least one cross-linking agent selected from phenolic compounds.

[0023] The inventors surprisingly found that the hybrid adhesive according to the present invention provides improved properties compared to pure PUF adhesives and pure protein adhesives.

[0024] In particular, the addition of a specific protein binder to the PUF binder can not only reduce ammonia emissions during processing, but also formaldehyde emissions, especially in the spinning chamber during the application of the binder to the mineral fibers.

[0025] Therefore, in PUF binders modified with ammonia as a formaldehyde scavenger, the addition of a protein binder not only leads to a dramatic reduction in ammonia emissions, but also significantly reduces formaldehyde emissions. Generally speaking, the reduction in ammonia emissions is greater than the degree of substitution of the PUF binder. The reduction in formaldehyde emissions is even more pronounced.

[0026] PUF adhesives that do not include ammonia as a formaldehyde scavenger remove most of the ammonia emissions, but also result in very high formaldehyde emissions. This formaldehyde emission from ammonia-free PUF adhesive can be greatly reduced by partially replacing it with a protein adhesive.

[0027] As a result, the mixture of the PUF binder of the present invention with a protein binder can reduce both ammonia and formaldehyde emissions compared to the pure PUF binder, which can also partially or completely remove ammonia from the PUF binder. Without wishing to be bound by any theory, it is hypothesized that these improvements are at least partially due to the very strong binding / crosslinking of the protein with formaldehyde.

[0028] Another benefit of reducing or omitting the amount of ammonia in the PUF adhesive by adding a protein binder is the reduction of the gelling tendency often encountered in these systems. This substitution allows avoiding the risk of gelling of the adhesive system.

[0029] Compared to pure PUF adhesives, the hybrid adhesives of the present invention generally maintain and in most cases even significantly improve the mechanical strength. In particular, the mechanical strength after aging treatment is generally significantly improved.

[0030] When starting with a protein binder, the addition of a PUF binder also resulted in significant improvements compared to the pure protein binder. As mentioned above, a disadvantage of protein binders is their relatively high solubility and water absorption in the cured state. However, even small amounts of PUF binder mixed into the protein binder, after curing, produced a virtually insoluble binder with low water absorption and very hard strips even after removal from an 80°C water bath. This demonstrates that the PUF binder is highly effective as a crosslinker for the protein binder.

[0031] The improvements described for mixed adhesives are such that they cannot generally be explained by additive effects but rather indicate a synergistic interaction between the two adhesive systems mixed.

[0032] DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] The present invention relates to an aqueous adhesive composition made from a mixture of the following substances:

[0034] i) a phenol-urea-formaldehyde binder (PUF binder), and

[0035] ii) a protein binder comprising at least one protein and at least one cross-linking agent selected from phenolic compounds.

[0036] The aqueous adhesive composition of the present invention is a hybrid adhesive composition obtained by mixing two separate adhesives, namely a phenol-urea-formaldehyde adhesive and a protein adhesive. Herein, the phenol-urea-formaldehyde adhesive is also referred to as a PUF adhesive, which is a common name for this type of adhesive system. The separate adhesives are generally complete adhesives that can be used as adhesives themselves.

[0037] The aqueous binder composition of the invention as well as both the PUF binder and the protein binder are particularly suitable as binders for mineral fibers for producing mineral fiber products.

[0038] The adhesive composition of the present invention is an aqueous adhesive composition, i.e., the adhesive composition comprises water. Typically, both PUF adhesives and protein adhesives are aqueous adhesives. If desired, water may be added to the mixture, for example, to adjust desired properties, such as viscosity.

[0039] PUF adhesive

[0040] Phenol-urea-formaldehyde binders (PUF binders) based on phenol-urea-formaldehyde resins (PUF resins) are well known to the skilled person and have a wide range of applications, for example as binders for mineral fibers in the production of mineral fiber products.

[0041] According to the present invention, the nature of the PUF binder is not critical and any PUF binder known in the art may be used. PUF binders that are mixtures of phenol formaldehyde binders (PF binders) and urea formaldehyde binders (UF binders) may also be used.

[0042] The raw materials used to prepare PUF adhesives based on PUF resins are typically phenol, urea, formaldehyde, and a base as a catalyst. Optionally, other materials can be used in the reaction, such as formaldehyde scavengers such as ammonia and hardeners such as ammonium salts (such as ammonium sulfate). Formaldehyde can be introduced into the reaction, for example, in the form of an aqueous solution (formalin) or paraformaldehyde.

[0043] The base used in the process of preparing the PUF resin or adhesive may include at least one basic alkali metal or alkaline earth metal compound or an amine catalyst, such as triethylamine (TEA). Examples of alkali metal bases that can be used include hydroxides of sodium, potassium, and lithium. Examples of alkaline earth metal bases that can be used include oxides and hydroxides of calcium, barium, and strontium, such as calcium oxide and calcium hydroxide.

[0044] The PUF binder used in the aqueous binder composition according to the present invention is typically a phenol-urea-formaldehyde resole binder. Resole or resole-type binders are obtained by using a stoichiometric excess of formaldehyde relative to phenol (i.e., a molar ratio of aldehyde to phenol greater than 1).

[0045] Specific examples of suitable PUF resol resins or binders are, for example, those disclosed in EP-A-148050, EP-A-810981, CA-A-1001788 and US-A-5371140; the emulsifiable phenolic resins disclosed in EP-A-1084167; the overcondensed phenolic resins disclosed in WO 99 / 03906 and WO 2009 / 136106.

[0046] The production of PUF binders or PUF resins typically involves the reaction of phenol and formaldehyde in an alkaline aqueous solution to produce a phenolic resin. Urea can be introduced during or after resin preparation to obtain a phenol-urea-formaldehyde resin.

[0047] In a preferred embodiment, the molar ratio of phenol to formaldehyde used to prepare the PUF adhesive is from 1:2.5 to 1:6; preferably from 1:3 to 1:5.

[0048] In a preferred embodiment, the amount of urea used to prepare the PUF adhesive is 20 wt% to 60 wt%, preferably 30 wt% to 50 wt%, based on the total weight of phenol, formaldehyde and urea used to prepare the PUF adhesive.

[0049] More specifically, after mixing phenol and aldehyde by adding a base to the aqueous solution, an exothermic condensation reaction of the phenol and aldehyde is initiated. For example, when a basic catalyst is added, the aqueous mixture of phenol and formaldehyde can be maintained at a first temperature, such as 40-50°C. The temperature can then be allowed to rise to a second reaction temperature, such as 60-90°C. In an alternative embodiment, the aqueous mixture of phenol and formaldehyde can be heated in the presence of a base at a continuous heating rate of, for example, 0.5-1.5°C / min, such as about 1°C / min, to a final temperature, such as 60-90°C, for example, about 84°C, and maintained at this final temperature for a certain period of time.

[0050] Preferably, the reaction of phenol with formaldehyde is carried out at a suitable temperature for a sufficient reaction time to provide a resin, preferably a resol resin, having an acid resistance of <8, preferably in the range of 0.5 to 7, more preferably in the range of 3 to 5. Acid resistance is a measure of the degree of reaction. A method for its determination is given in the experimental section below.

[0051] The conversion of phenol is preferably >95%, more preferably >97%.

[0052] Urea can be added to the resin during its preparation, especially resol resin, or in a post-reaction step.

[0053] A hardening agent, such as ammonium sulfate or an acid, such as sulfuric acid, may be added to the reaction mixture.

[0054] The PUF resin or PUF adhesive may be a PUF resin or PUF adhesive modified with ammonia, or it may be a PUF resin or PUF adhesive not modified with ammonia. Preferably, the PUF adhesive is not modified with ammonia. As described above, ammonia can act as a formaldehyde scavenger. Modification of the PUF resin or PUF adhesive with ammonia is performed by adding ammonia (e.g., in gaseous form, but typically in the form of an aqueous ammonia solution) to the reaction material or PUF resin, preferably after formation of the phenol-urea-formaldehyde resin or phenol-urea-formaldehyde resol resin. It should be noted that the ammonia referred to here refers only to ammonia itself, i.e., it does not include ammonium salts that may be added as additives. This also applies to the following instructions regarding suitable amounts.

[0055] In a preferred embodiment, the amount of ammonia is 0% to 6% by weight, more preferably 0% to 4% by weight, and even more preferably 0% to 3% by weight, based on the solids of the binder component of the PUF binder. As described above, the PUF binder is more preferably not modified with ammonia, i.e., the amount of ammonia is 0%. When the PUF binder or PUF resin is modified with ammonia, a suitable lower limit for the amount of ammonia can be, for example, at least 0.1% by weight, based on the solids of the binder component of the PUF binder. Thus, when modified with ammonia, the amount of ammonia can be, for example, 0.1% to 6% by weight, preferably 0.5% to 4% by weight, and even more preferably 1% to 3% by weight, based on the solids of the binder component of the PUF binder. The solids of the binder component of the PUF binder are defined below in the description of the mixture.

[0056] The obtained aqueous composition containing a PUF resin, preferably a PUF resol resin, can be used as the PUF adhesive of the aqueous adhesive composition of the present invention. Optionally, water can be added to adjust the viscosity of the PUF adhesive. In addition, additives can be optionally added to the PUF adhesive.

[0057] Protein binders

[0058] The second binder used in the hybrid aqueous composition of the present invention is a protein binder comprising i) at least one protein and iii) at least one cross-linking agent selected from phenolic compounds.

[0059] Protein adhesives are typically water-based adhesives. In addition, protein adhesives are typically formaldehyde-free adhesives. The adhesive may contain one or more proteins.

[0060] For the purposes of this application, the term "formaldehyde-free" is defined as characterizing a mineral wool product wherein the formaldehyde emissions from the mineral wool product are below 5 μg / m2 / h, preferably below 3 μg / m2 / h. Preferably, the test is performed according to ISO 16000 for testing aldehyde emissions.

[0061] Preferably the pH of the protein binder is in the range of 4.5 to 9.5, preferably 5.0 to 8.0 or 6.0 to 8.0.

[0062] protein

[0063] The protein of the protein binder can be selected from proteins of animal origin; proteins from jellyfish, proteins produced by recombinant technology; proteins from insects; proteins of plant origin, including gluten and mussel foot protein. The protein is preferably selected from proteins of animal origin, such as collagen, gelatin, hydrolyzed gelatin, and proteins of plant origin, such as gluten, or combinations thereof.

[0064] In a preferred embodiment, the protein of the protein binder used in the aqueous adhesive composition according to the present invention is selected from the group consisting of: proteins of animal origin, including collagen, gelatin, hydrolyzed gelatin and proteins from milk (casein, whey), eggs; proteins from jellyfish, proteins produced by recombinant technology; proteins from insects such as silkworms, such as sericin; proteins of plant origin, including gluten, proteins from algae, legumes, cereals, whole grains, nuts, seeds and fruits, such as proteins from buckwheat, oats, rye, millet, maize (corn), rice, wheat, bulgur, sorghum, amaranth, quinoa, soybeans (soy protein), lentils, kidney beans, white beans, mung beans, chickpeas, cowpeas, lima beans, pigeon peas, lupines, winged beans, almonds, Brazil nuts, cashews, pecans, walnuts, rapeseed, cottonseed, pumpkin seeds, sesame seeds and sunflower seeds, proteins produced by recombinant technology; mussel foot protein or a combination thereof.

[0065] In one embodiment, the protein binder comprises at least two proteins, wherein one protein is at least one selected from the group consisting of proteins of animal origin: including collagen, gelatin, hydrolyzed gelatin and proteins from milk (casein, whey), eggs; proteins from jellyfish, proteins produced by recombinant technology; proteins from insects such as silkworms, such as sericin, such as mussel foot protein; and the other protein is at least one selected from the group consisting of proteins of plant origin: including gluten, proteins from algae, legumes, cereals, whole grains, nuts, seeds and fruits, such as proteins from buckwheat, oats, rye, millet, maize (corn), rice, wheat, bulgur, sorghum, amaranth, quinoa, soybeans (soy protein), lentils, kidney beans, white beans, mung beans, chickpeas, cowpeas, lima beans, pigeon peas, lupines, winged beans, almonds, Brazil nuts, cashews, pecans, walnuts, rapeseed, cottonseed, pumpkin seeds, sesame seeds and sunflower seeds.

[0066] In one embodiment the protein binder does not comprise protein from soy (soy protein).In one embodiment the protein comprised in the protein binder comprises 50 to 400, such as 100 to 300 (hydroxyproline + proline) residues per 1000 amino acid residues.

[0067] Preferably, the at least one protein comprises or is selected from collagen, gelatin, hydrolyzed gelatin, gluten or a combination thereof.

[0068] In a more preferred embodiment, the at least one protein comprises or is gelatin, gluten, or a combination thereof, with gelatin being most preferred.

[0069] Collagen is a very abundant substance in living tissue: it is the major component of connective tissue and constitutes 25-35% of the total protein content of mammals.

[0070] Gelatin is derived from the chemical degradation of collagen. Gelatin can also be produced through recombinant technology. Gelatin is water-soluble and typically has a molecular weight of 10,000 to 500,000 g / mol, such as 30,000 to 300,000 g / mol, depending on the degree of hydrolysis. Gelatin is a widely consumed food, and it is generally accepted that this compound is completely non-toxic, so no precautions are required when handling it.

[0071] Gelatin is a heterogeneous mixture of single- or multi-chain polypeptides that typically exhibit a helical structure. Specifically, the triple helix of type I collagen, which is extracted from skin and bone and is used as a source of gelatin, consists of two α1(I) chains and one α2(I) chain.

[0072] Gelatin solutions can undergo a coiled-coil transition. Type A gelatin is produced by acid treatment. Type B gelatin is produced by alkaline treatment.

[0073] Chemical cross-linking can be introduced into gelatin. In one embodiment, transglutaminase is used to link lysine to glutamine residues; in one embodiment, glutaraldehyde is used to link lysine to lysine, and in one embodiment, tannin is used to link nucleophilic residues, such as lysine residues.

[0074] Gelatin can also be further hydrolyzed into smaller fragments down to 3000 g / mol.

[0075] When the gelatin solution is cooled, collagen-like helices can be formed. Gelatin can form helical structures. In one embodiment, the solidified adhesive comprising a protein comprises a helical structure.

[0076] In one embodiment, at least one protein is a low strength gelatin, such as a gelatin having a gel strength of 10 to 125 Bloom. In one embodiment, at least one protein is a medium strength gelatin, such as a gelatin having a gel strength of 125 to 180 Bloom. In one embodiment, at least one protein is a high strength gelatin, such as a gelatin having a gel strength of 180 to 300 Bloom.

[0077] In a preferred embodiment, the gelatin is derived from one or more sources selected from the group consisting of: mammalian, avian species, such as from cattle, pigs, horses, poultry, and / or from fish scales, fish skin.

[0078] Gluten is a structural protein naturally present in the grains of certain cereals, such as wheat (e.g., common wheat, durum wheat, spelt, Khorasan wheat, emmer wheat, and einkorn wheat); barley; rye; and some oat cultivars. Gluten is a general term for a family of proteins. The main types of these proteins are gliadin and glutenin. The corresponding wheat proteins are called glutenins (for gluten) and gliadin (for alcohol-soluble proteins), which can be further divided into high- and low-molecular-weight glutenins, as well as α / β, γ, and omega prolamins. Gluten typically makes up 75-85% of the total protein content of bread wheat.

[0079] Without wishing to be bound by any particular theory, the inventors of the present invention believe that the surprisingly good results obtained are at least partially due to a denaturation process of at least one protein in the protein binder that may occur during the curing process. Denaturation is the process by which a protein loses its quaternary, tertiary, and / or secondary structure present in its native state.

[0080] In one embodiment, urea may be added to the adhesive composition according to the present invention. The inventors have found that even small amounts of urea can cause gelatin denaturation, which can slow gelation, which may be desirable in some embodiments. The addition of urea may also cause the product to soften.

[0081] The inventors have found that the carboxylic acid groups in gelatin interact strongly with trivalent and tetravalent ions (e.g., aluminum salts). This is particularly true for type B gelatin, which contains more carboxylic acid groups than type A gelatin.

[0082] Cross-linking agent selected from phenolic compounds

[0083] The protein binder used as the second binder of the aqueous binder composition according to the present invention further comprises at least one cross-linking agent selected from phenolic compounds, in particular one or more phenolic compounds.

[0084] The present inventors have discovered that a variety of such phenolic compounds can be used in protein adhesives. Typically, these phenolic compound components are obtained from plant tissue and are therefore renewable materials. In some embodiments, the compounds are also non-toxic and non-corrosive. Another advantage is that these compounds are antimicrobial, thereby imparting their antimicrobial properties to mineral wool products bonded with such adhesives.

[0085] Phenolic compounds, or phenolic compounds, are compounds with one or more hydroxyl groups directly attached to an aromatic ring. Polyphenols (also known as polyhydroxyphenols) are compounds with more than one phenolic hydroxyl group attached to one or more aromatic rings. Phenolic compounds, or phenolic compounds, are characteristic of plants and, as a group, are usually present as esters or glycosides rather than as free compounds.

[0086] The term phenolic compound encompasses a large number of different compounds. Preferably, the phenolic compound is a compound according to the scheme based on the number of carbons in the molecule as detailed by W. Vermerris, R. Nicholson in Phenolic Compound Biochemistry, Springer Netherlands, 2008.

[0087] In one embodiment, the phenolic compound is selected from the group consisting of simple phenols, phenolic compounds having a structure more complex than a C6 structure, such as oligomers of simple phenols, polyphenols (polyhydroxyphenols). The phenolic compound is preferably a polyphenol or a polyhydroxyphenol, respectively.

[0088] Examples of the at least one phenolic compound are phenolic compounds selected from the group consisting of simple phenolic compounds such as hydroxybenzoic acid, hydroxybenzaldehyde, hydroxyacetophenone, hydroxyphenylacetic acid, cinnamic acid, cinnamate, cinnamaldehyde and cinnamyl alcohol; coumarins such as isocoumarins; chromones; flavonoids; chalcones such as dihydrochalcone; aurone; flavanones such as flavanols; flavans; leucocyanidins; flavan-3-ols; flavones; anthocyanidins; deoxyanthocyanidins; anthocyanins; biflavonoids; benzophenones; xanthones; stilbenes; betacyanins; polyphenols and / or polyhydroxyphenols, such as lignans, neolignans (dimers or oligomers obtained by coupling lignin monomers such as p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol), lignins (synthesized mainly from lignin monomer precursors p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol), tannins, such as tannates (salts of tannins), condensed tannins (proanthocyanidins), hydrolyzed tannins, gallic tannins, ellagitannins, complex tannins, tannic acid, phlobabenes, such as brown algae polyphenols (Phlorotannins); compounds containing sulfonated phenols and combinations thereof.

[0089] In one embodiment, the phenolic compound according to the present method is a quinone. Quinones are oxidized derivatives of aromatic compounds and are generally readily prepared from reactive aromatic compounds such as phenols having electron-donating substituents. Quinones useful in the present invention include benzoquinones, naphthoquinones, anthraquinones, and lawsone.

[0090] Tannins comprise a group of compounds with a wide range of structural diversity that share their ability to bind / crosslink and precipitate proteins. Tannins are abundant in many different plant species, particularly oak, chestnut, staghorn sumac, and tassel cup. Tannins can be found in leaves, bark, and fruit. Tannins can be divided into three categories: condensed tannins, hydrolyzed tannins, and complex tannins. Condensed tannins, or proanthocyanidins, are oligomeric or polymeric flavonoids composed of flavan-3-ol (catechin) units. Gallotannins are hydrolyzed tannins whose polyol core is substituted with 10 to 12 gallic acid residues. The most common polyol in gallotannins is D-glucose, although some gallotannins contain catechin and triterpenoid units as core polyols. Ellagitannins are hydrolyzed tannins that differ from gallotannins in that they contain additional C-C bonds between adjacent galloyl moieties. Complex tannins are defined as tannins in which a catechin unit is glycosidically bonded to a gallotannin or ellagitannin unit.

[0091] In a particularly preferred embodiment, the at least one phenolic compound comprises or is a tannin. The tannin is preferably selected from one or more of the group consisting of tannic acid, condensed tannins (proanthocyanidins), sulfonated tannins, hydrolyzed tannins, gallic tannins, ellagitannins, complex tannins and / or tannins derived from one or more of oak, chestnut, staghorn sumac, fringed cup grass, sackwood, acacia, mimosa, black wattle bark, grape, gallnut, black tea, terminalia chebula, vesica oleracea, oak and eucalyptus.

[0092] In particularly preferred embodiments of the protein binder, the at least one protein comprises or is gelatin, gluten, or a combination thereof, and the at least one phenolic compound comprises or is tannin.

[0093] Preferably, the content of the at least one phenolic compound in the protein binder is in the range of 1 wt.% to 30 wt.%, more preferably 2 wt.% to 15 wt.%, most preferably 3 wt.% to 10 wt.%, based on the dry weight of the at least one protein, wherein in preferred amounts, the at least one phenolic compound is tannin and / or the at least one protein is gelatin.

[0094] Glyceryl fatty acid esters

[0095] In a preferred embodiment, the protein binder as the second component of the aqueous binder composition of the present invention further comprises at least one glycerol fatty acid ester.

[0096] If the glycerol fatty acid ester is contained in the protein binder, the content of the glycerol fatty acid ester is preferably 0.6% to 30% by weight, more preferably 2% to 10% by weight, and even more preferably 3% to 7.5% by weight, based on the dry weight of the at least one protein and the at least one phenolic compound.

[0097] Fatty acids are carboxylic acids with saturated or unsaturated fatty chains. Glycerol is a polyol compound whose IUPAC name is propane-1,2,3-triol. Naturally occurring fats and oils are glycerol esters (also known as triglycerides) of fatty acids. For the purposes of this invention, the term glycerol fatty acid esters refers to monoesters, diesters, and triesters of glycerol with fatty acids.

[0098] Although the term fatty acid in the present description may be any carboxylic acid having an aliphatic chain, it is preferably a carboxylic acid having an aliphatic chain of 4 to 28 carbon atoms, preferably an even number of carbon atoms. Preferably, the fatty chain of the fatty acid is unbranched.

[0099] In a preferred embodiment, the at least one glycerol fatty acid ester is in the form of a vegetable oil and / or an animal oil.In the present description, the term "oil" includes at least one glycerol fatty acid ester in the form of an oil or a fat.

[0100] In a preferred embodiment, the at least one fatty acid ester of glycerol is in the form of a pulp fat such as palm oil, olive oil, avocado oil; a kernel fat such as lauric oils such as coconut oil, palm kernel oil, babassu oil and other palm seed oils, other sources of lauric oils; a palmitic-stearic oil such as cocoa butter, shea butter, Borneo butter and related fats (margarines); a palmitic oil such as cottonseed oil, kapok oil and related oils, pumpkin seed oil, corn (maize) oil, cereal oils; an oleic-linoleic oil such as sunflower oil, sesame oil, linseed oil, perilla oil, tea seed oil, safflower oil and black seed oil. oil), grapeseed oil, poppyseed oil, leguminous oils such as soybean oil, peanut oil, lupin oil; cruciferous oils such as rapeseed oil, mustard oil; conjugated acid oils such as tung oil and related oils, oti oil and related oils; substituted fatty acid oils such as castor oil, Indian celery oil, celery oil and gorlioil, vernonia oil; animal fats such as terrestrial animal fats such as lard, tallow, mutton tallow, horse oil, goose oil, chicken oil; marine oils such as whale oil and fish oil.

[0101] In a preferred embodiment, the at least one glycerol fatty acid ester is in the form of a vegetable oil, in particular one or more components selected 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, with linseed oil being particularly suitable.

[0102] In one embodiment, at least one glycerol fatty acid ester is not of natural origin. In one embodiment, at least one glycerol fatty acid ester is a vegetable oil or animal oil of modification. In one embodiment, at least one glycerol fatty acid ester comprises at least one trans fatty acid. In alternative preferred embodiments, at least one glycerol fatty acid ester is in the form of animal oil, such as fish oil.

[0103] In a preferred embodiment, the protein binder comprises at least one protein (which is or includes gelatin) and at least one cross-linking agent (which is or includes a phenolic compound that is a tannin) and at least one glycerol fatty acid ester (such as at least one fatty acid ester of a glyceride of one or more components selected 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).

[0104] The present inventors have discovered that a parameter of the glycerol fatty acid esters used in protein binders, namely the amount of unsaturation in the fatty acids, can be used to distinguish preferred embodiments. The amount of unsaturation in fatty acids is typically measured by the iodine value (also known as the iodine value, iodine absorption value, or iodine index). The higher the iodine value, the more C=C bonds are present in the fatty acid. To determine the iodine value as a measure of fatty acid unsaturation, we refer to Thomas, Alfred (2012) "Fats and fatty oils" in Ullmann's Encyclopedia of industrial chemistry, Weinheim, Wiley-VCH.

[0105] In a preferred embodiment, the at least one glycerol fatty acid ester comprises a vegetable oil and / or animal oil having an iodine value of ≥75, such as 75 to 180, such as ≥130, such as 130 to 180. In an alternative preferred embodiment, the at least one glycerol fatty acid ester comprises a vegetable oil and / or animal oil having an iodine value of ≤100, for example ≤25.

[0106] In a preferred embodiment, the at least one glycerol fatty acid ester is selected from one or more components of the group consisting of: vegetable oils with an iodine value in the range of about 136 to 178, such as linseed oil with an iodine value in the range of about 136 to 178, vegetable oils with an iodine value in the range of about 80 to 88, such as olive oil with an iodine value in the range of about 80 to 88, vegetable oils with an iodine value in the range of about 163 to 173, such as tung oil with an iodine value in the range of about 163 to 173, vegetable oils with an iodine value in the range of about 7 to 10, such as coconut oil with an iodine value in the range of about 7 to 10, vegetable oils with an iodine value in the range of about 140 to 170, vegetable oils with an iodine value in the range of about 94 to 120, such as rapeseed oil with an iodine value in the range of about 94 to 120, vegetable oils with an iodine value in the range of about 118 to 144, such as sunflower oil with an iodine value in the range of about 118 to 144.

[0107] In one embodiment, the at least one glycerol fatty acid ester is a drying oil. For a definition of drying oils, see Poth, Ulrich (2012) "Drying oils and related products" in Ullmann's Encyclopedia of industrial chemistry, Weinheim, Wiley-VCH.

[0108] In one embodiment, the at least one glycerol fatty acid ester is selected from one or more components of the group consisting of linseed oil, olive oil, tung oil, coconut oil, rapeseed oil, and sunflower oil.

[0109] Therefore, the present inventors have found that when the iodine value is within a relatively high range or, alternatively, within a relatively low range, particularly good results can be obtained. Although not wishing to be bound by any particular theory, the present inventors hypothesize that the advantageous properties brought about by fatty acid esters with high iodine values on the one hand and fatty acid esters with low iodine values on the other hand are based on different mechanisms. The present inventors hypothesize that the advantageous properties of fatty acid glycerides with high iodine values may be attributed to the participation of C=C double bonds present in large quantities in these fatty acids in the cross-linking reaction, while fatty acid glycerides with low iodine values and lacking a large number of C=C double bonds may stabilize the cured adhesive through van der Waals interactions. The present inventors hypothesize that the polar end of the fatty acid glyceride interacts with the polar region of at least one protein, while the non-polar end interacts with the non-polar region of at least one protein.

[0110] Containing divalent metal cations M 2+ Compounds

[0111] In one embodiment, the protein binder as the second component of the aqueous binder composition of the present invention may further comprise at least one divalent metal cation containing M2+ of compounds.

[0112] Without wishing to be bound by any particular theory, the present inventors believe that the reaction between phenolic compounds and proteins relies at least in part on the oxidation of phenols to quinones, followed by nucleophilic attack of nucleophilic groups such as amine and / or thiol groups in the protein, which results in cross-linking and / or modification of the protein by the phenolic compound. 2+ The improvement brought about by the presence of the compound can be explained by the chelation effect, where M 2+ The negatively charged groups of the cross-linked proteins are cross-linked.

[0113] The at least one divalent metal cation M 2+ The compound comprises one or more divalent metal cations M 2 + , which is selected from alkaline earth metals such as Ca 2+ , divalent cations of Mn, Fe, Cu, Zn, and Sn.

[0114] In one embodiment, the at least one divalent metal cation compound is included in the protein binder in an amount of 0.1 wt % to 10 wt %, such as 0.2 wt % to 8 wt %, such as 0.3 wt % to 5 wt %, such as 0.4 wt % to 4.3 wt %, such as 1.0 wt % to 4.3 wt %, based on the combined dry weight of the at least one phenolic compound and the at least one protein.

[0115] Other additives

[0116] The protein binder may optionally contain one or more other additives. Examples of such additives are oxidizing agents, such as tyrosinase, pH adjusters, preferably in the form of a base, such as an organic base, such as an amine or a salt thereof, an inorganic base, such as lithium hydroxide, sodium hydroxide, and / or potassium hydroxide. If used, the amount of other additives in the protein binder may range from 0.01% to 15% by weight, or from 0.01% to 10% by weight, preferably from 0.05% to 6% by weight, based on the combined dry weight of the at least one phenolic compound and the at least one protein.

[0117] Hybridization of PUF binder and protein binder

[0118] The aqueous adhesive composition of the present invention can be obtained by, for example, adding the protein adhesive to the PUF adhesive or vice versa and, if necessary, mixing the obtained mixture with a mixing device. Conventional mixing devices such as mixing tanks or static mixers can be used.

[0119] In order to obtain the aqueous adhesive composition of the present invention, the PUF adhesive and the protein adhesive are preferably mixed in such a ratio that the weight proportion B is 5 wt % to 95 wt %, more preferably 10 wt % to 90 wt %, based on the total weight of A+B, wherein B is the weight of the adhesive component solids of the protein adhesive and A is the weight of the adhesive solids of the PUF adhesive.

[0120] The weight proportion B may suitably be, for example, in the range of 15% to 90% by weight, preferably 20% to 90% by weight, based on the total weight of A+B.

[0121] Depending on whether a PUF binder or a protein binder is the main component of the aqueous binder composition of the present invention, the present invention can also be used to improve the properties of the PUF binder or the protein binder.

[0122] Therefore, when the PUF adhesive is the main component of the aqueous adhesive composition of the present invention, the weight proportion B is preferably in the range of 5 wt % to 50 wt %, more preferably 10 wt % to 45 wt %, still more preferably 15 wt % to 40 wt % or 20 wt % to 40 wt % or 25 wt % to 40 wt %, based on the total weight of A + B.

[0123] As can be seen in the experimental section below, incorporating even a low proportion of protein binder into the PUF binder leads to a significant reduction in ammonia and formaldehyde emissions from the PUF binder modified with ammonia, as well as a significant reduction in formaldehyde emissions from the PUF binder not modified with ammonia, compared to the neat binder.

[0124] In the case where the protein binder is the main component of the aqueous binder composition of the present invention, the weight proportion of B is preferably in the range of 50 wt % to 95 wt %, more preferably 60 wt % to 90 wt %, and more preferably 70 wt % to 90 wt %, based on the total weight of A + B. In other words, the weight proportion of A is preferably in the range of 5 wt % to 50 wt %, more preferably 10 wt % to 40 wt %, and more preferably 10 wt % to 30 wt %, based on the total weight of A + B.

[0125] As can be seen in the experimental section below, incorporating even low ratios of PUF binder into protein binders results in significantly reduced binder solubility and water uptake in the resulting binders compared to the pure protein binder.

[0126] Furthermore, the aqueous binder composition of the invention allows the mineral fiber products produced with the binder of the invention to have very good mechanical strength compared to both pure PUF binders and pure protein binders. Thus, when compared to the PUF reference, the mechanical strength of the unaged products shows a similar slight decrease and, in most cases, even a significant increase, while the mechanical strength of the aged products is generally significantly increased.

[0127] In one embodiment, the total amount of the PUF binder, the at least one protein, and the at least one cross-linking agent selected from phenolic compounds in the aqueous binder composition is in the range of 75 wt % to 100 wt %, preferably 85 wt % to 97 wt %, based on the total weight of the binder solids of the PUF binder and the binder component solids of the protein binder.

[0128] In the specification of the present application, "binder component solids" and "binder solids" are defined as follows.

[0129] Binder component solids content - definition

[0130] The weight content of each component in a given adhesive solution before curing is based on the anhydrous mass of each component, i.e. without solvents, especially water. The following formula can be used:

[0131]

[0132] In the case of PUF adhesives, formaldehyde and ammonia (if used) are also considered components of the adhesive. Although these raw materials are volatile, they are at least partially reacted during the preparation of the PUF resin.

[0133] Adhesive Solids - Definition and Procedure

[0134] The weight content of the adhesive after curing is referred to as "adhesive solids."

[0135] A disc-shaped asbestos sample (5 cm in diameter, 1 cm in height) was cut from the asbestos and heat-treated at 590°C for at least 30 minutes to remove all organic matter. The adhesive solids were measured by distributing an adhesive sample (approximately 2 g) onto the heat-treated asbestos disc in a tinfoil container. The tinfoil container containing the asbestos disc was weighed immediately before and after the adhesive was added. Two such adhesive-laden asbestos discs were prepared in the tinfoil container and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the sample was weighed, and the adhesive solids were calculated as the average of the two results.

[0136] Method for producing mineral fiber products

[0137] The present invention also relates to a method for producing a mineral fiber product, comprising the steps of contacting mineral fibers with an aqueous binder composition according to the invention and curing the binder.

[0138] The aqueous adhesive composition according to the present invention has been described above. Of course, all the above descriptions of the aqueous adhesive composition also apply to the aqueous adhesive composition used in the method of the present invention.

[0139] Mineral fibers can be, for example, any man-made glass fibers (MMVF), glass fibers or glass wool, ceramic fibers, basalt fibers, slag fibers, rock fibers or asbestos, etc. These fibers can be in the form of wool products, such as, for example, asbestos products or glass wool products.

[0140] The step of contacting the mineral fibres with the aqueous binder composition may be achieved by applying the aqueous binder composition to the mineral fibres by conventional means, for example by spraying.

[0141] Curing of the aqueous binder composition in contact with the mineral fibers may be carried out in a wide temperature range, such as from room temperature to 250°C, for example in the range of 15 to 250°C, preferably 150 to 250°C, more preferably 175 to 225°C.

[0142] The curing process may begin immediately after the binder is applied to the fibers. In one embodiment, curing is carried out in a curing apparatus, such as in a conventional curing oven or hot press.

[0143] In one embodiment, the curing process includes a drying process. In one embodiment, the curing process includes pressurized drying. Pressure can be applied by blowing air or gas into the mixture of mineral fibers and binder. The blowing process can be accompanied by heating or cooling, or it can be carried out at ambient temperature.

[0144] Mineral fibers are usually produced in fiber forming apparatuses in which a mineral melt is spun from an apparatus such as a cupspinning apparatus or a cascade spinning apparatus to form the mineral fibers. The formed mineral fibers are preferably introduced into a spinning chamber.

[0145] In a preferred embodiment, in either case, the aqueous binder composition is applied to the vicinity of the fiber forming apparatus, such as a cup spinner or a cascade spinner, immediately after fiber formation. Thus, the aqueous binder composition is preferably applied to the mineral fibers formed in the spinning chamber, preferably by spraying. Thereafter, the fibers coated with the binder are typically transported as a web, such as a collected web, to a conveyor belt. The web, such as a collected web, may be subjected to longitudinal or lengthwise compression after fiber formation and before substantial curing occurs.

[0146] In a preferred embodiment, the method for producing a mineral fiber product according to the present invention comprises the following steps:

[0147] - manufacture of melts of raw materials,

[0148] - fiberizing the melt to form mineral fibers by means of a fiber-forming device, wherein the formed mineral fibers are preferably introduced into a spinning chamber,

[0149] - providing the mineral fibers in the form of a collected web,

[0150] - applying an aqueous binder composition to the mineral fibers before, during or after providing the collected web to form a mixture of mineral fibers and the binder composition, wherein the aqueous binder composition is preferably applied by spraying before providing the collected web, preferably in the spinning chamber,

[0151] - Curing the binder composition mixed with the mineral fibers.

[0152] There are various types of centrifugal rotors used as fiber forming devices for fiberizing mineral melts.

[0153] Conventional centrifugal spinners are cascade spinners that include a series of top (or first) rotors and subsequent (or second) rotors and optionally other subsequent rotors (such as third and fourth rotors). Each rotor rotates about a different, substantially horizontal axis, with a direction of rotation opposite to that of the rotor or each adjacent rotor in the sequence. The different horizontal axes are arranged so that the melt poured onto the top rotor is sequentially thrown onto the outer peripheral surface of the subsequent rotor or each subsequent rotor, and the fiber is thrown out of the subsequent rotor or each subsequent rotor, and optionally also out of the top rotor.

[0154] In one embodiment, a cascade spinner or other rotor is arranged to fiberize the melt, and the fibers are entrained in the air as a cloud of fibers.

[0155] Many fiber forming devices include a disc or cup that rotates around a substantially vertical axis. Several of these spinners are then typically arranged in a straight line, i.e., substantially in a first direction, as described, for example, in GB-A-926,749, US-A-3,824,086, and WO-A-83 / 03092.

[0156] There is typically an air flow associated with the or each fiberizing rotor whereby the fibres are entrained in the air as they are formed off the rotor surface.

[0157] In one embodiment, the aqueous binder composition of the present invention and / or additives are added to the fiber cloud by known methods. The amount of binder and / or additives may be the same or different for each spinner.

[0158] As used herein, the term "collected web" is intended to include any mineral fibers that have been collected together on a surface (i.e., they are no longer entrained in the air), such as fiberized mineral fibers, granules, tufts, or recycled web waste. The collected web may be a primary web formed by collecting fibers on a conveyor belt and provided as a starting material without cross-lapping or otherwise consolidating.

[0159] Alternatively, the collecting web may be a secondary web formed by cross-lapping or otherwise consolidating primary webs.Preferably, the collecting web is a primary web.

[0160] Mineral fiber products

[0161] The present invention also relates to a mineral fiber product comprising mineral fibers bonded by a binder obtained by curing the aqueous binder composition of the present invention.The mineral fiber product of the present invention is preferably obtainable by the process according to the present invention.

[0162] The aqueous binder composition and method according to the present invention have been described above. All the above descriptions of the aqueous binder composition and method such as mineral fibers also apply to the mineral fiber product of the present invention.

[0163] In a preferred embodiment, the density of the mineral fiber product is between 10 and 1200 kg / m 3 , such as 30-800kg / m 3 , such as 40-600kg / m 3 , such as 50-250kg / m 3 , such as 60-200kg / m 3 within the range.

[0164] In a preferred embodiment, the mineral fiber product according to the invention is an insulation product, such as a thermal or acoustic insulation product, in particular having a density of 10 to 200 kg / m 3 density.

[0165] In an alternative embodiment, the mineral fiber product according to the invention is a cladding board, in particular having a density of 1000-1200 kg / m 3 density.

[0166] In preferred embodiments, the loss on ignition (LOI) of the mineral fiber product according to the invention is in the range of 0.1 to 25.0 wt%, such as 0.3 to 18.0 wt%, such as 0.5 to 12.0 wt%, such as 0.7 to 8.0 wt%.

[0167] The mineral fibre product may be in any conventional configuration, such as a mat or board, and may be cut and / or shaped (eg into pipe sections) before, during or after curing of the binder.

[0168] application

[0169] The invention also relates to the use of the aqueous binder composition according to the invention for producing mineral fiber products.

[0170] The present invention also relates to the use of a protein binder in a phenol-urea-formaldehyde binder (PUF binder), comprising at least one protein and at least one crosslinker selected from phenolic compounds, to reduce at least one of formaldehyde and ammonia emissions during the application of the resulting aqueous binder composition to mineral fibers in a spinning chamber, compared to the application of the PUF binder to the mineral fibers in the spinning chamber without the addition of the protein binder. The use according to the invention is preferably carried out in the process according to the invention as described above.

[0171] The present invention also relates to the use of a phenol-urea-formaldehyde binder (PUF binder) in a protein binder comprising a combination of at least one protein and at least one crosslinker selected from phenolic compounds to reduce the water absorption of a mineral fiber product produced from the aqueous binder composition obtained and mineral fibers, compared to the water absorption of a mineral fiber product produced from a protein binder without the addition of the PUF binder. The use according to the invention is preferably carried out in the process according to the invention as described above.

[0172] The present invention also relates to a method for reducing formaldehyde and / or ammonia emissions during the application of a phenol-urea-formaldehyde binder (PUF binder) to mineral fibers in a spinning chamber, the method comprising the steps of adding a protein binder comprising at least one protein and at least one crosslinker selected from phenolic compounds to the PUF binder, and applying the resulting aqueous binder composition to the mineral fibers in the spinning chamber instead of the PUF binder. The method for reducing formaldehyde and / or ammonia emissions according to the invention is preferably a method for producing a mineral fiber product according to the invention.

[0173] The present invention also relates to a method for reducing the water absorption of a mineral fiber product bonded with a cured protein binder comprising a combination of at least one protein and at least one crosslinking agent selected from phenolic compounds, the method comprising the steps of adding a phenol-urea-formaldehyde binder (PUF binder) to the protein binder, applying the resulting aqueous binder composition to the mineral fibers instead of the protein binder, and curing the applied binder to obtain the mineral fiber product. The method for reducing water absorption according to the invention is preferably a method for producing the mineral fiber product according to the invention.

[0174] The aqueous binder composition, method and mineral fiber product according to the present invention have been described above. All the above descriptions of the aqueous binder composition, method and mineral fiber product also apply to the above-mentioned use and method of the present invention. Example

[0175] In the following examples, several adhesives falling within the definition of the present invention were prepared and compared to prior art adhesives.

[0176] Experimental methods and definitions

[0177] General experimental methods

[0178] Technical grade gelatin (from hides, skins, and bones, 150-180 bloom at 12.5%, 30 bloom at 6.67%) was obtained from Cam Moreu SA. Gluten protein was obtained from Crespel & Deiters GmbH & Co. KG. Mimosa tannin (Seta Sun, mimosa extract) was obtained from Otto Dille. Firnis linseed oil was obtained from OLI-NATURA. 40% Silane (Momentive VS-142 (aminoalkylsilane hydrolyzate in water) was provided by Momentive. A 28% aqueous ammonia solution and all other components were obtained in high purity from Sigma-Aldrich or TCI. For simplicity, all components without a specified concentration were assumed to be completely pure and anhydrous.

[0179] Using a Mettler Toledo pH measurements were performed using a Mettler Toledo SevenCompactTM S220 pH meter with an Expert Pro-ISM pH electrode and a temperature probe.

[0180] In the production of stone fibers, coarse stone pellets (mainly round particles with the same melt composition as stone fibers) formed during the cascade spinning process of stone melt are obtained from the ROCKWOOL plant in the Netherlands. Cleaned and sieved stone pellets suitable for making composite strips are produced from these coarse stone pellets by ProChem GmbH in Germany. Briefly, the stone pellets are heat treated overnight at 590°C to remove any traces of organic matter. After cooling, the stone pellets are sieved through 0.50 mm and 0.25 mm sieves. The coarse and fine fractions are discarded and the remaining stone pellets are washed thoroughly several times in demineralized water. The sieved and cleaned stone pellets are dried and then stored in sealed bags until use. In the following, the stone pellets obtained are simply referred to as pellets.

[0181] FUNKTION heat-resistant silicone templates used to make the strips (4×5 slots per template; slot top dimensions: length = 5.6 cm, width = 2.5 cm; slot bottom dimensions: length = 5.3 cm, width = 2.2 cm; slot height = 1.1 cm) were obtained from F&H of Scandinavia A / S.

[0182] Three-point bending tests were recorded on a Bent Tram SUT 3000 / 520 testing machine (test speed: 10.0 mm / min; rupture level: 50 N; nominal strength: 30 N / mm 2 Support distance: 40mm; Maximum deflection 20mm; Nominal elastic modulus (nominal E-modulus) is 10000N / mm 2 ). Place the strip in the machine with the "top" side facing up (ie the side with the dimensions length = 5.6 cm, width = 2.5 cm).

[0183] New tinfoil containers used for measuring adhesive solids (Comparative Adhesive A only) and loss on ignition of composite bars were heat treated at 590°C for 15 minutes prior to use to remove all organic matter.

[0184] An open heated tube oven apparatus was used to generate simulated spinning chamber emissions. Emissions generated by adhesive samples placed in a tube furnace at a given temperature were measured by drawing a constant stream of air through the sample through a heated tube to a MKS2030 FTIR gas analyzer. Spectral data were analyzed using Series 2000 Multigas analyzer software (version 10.4).

[0185] Binder component solids content - definition

[0186] The weight content of each component in a given adhesive solution before curing is based on the anhydrous mass of each component, i.e. without solvents, especially water. The following formula can be used:

[0187]

[0188] In the case of PUF adhesives, formaldehyde and ammonia (if used) are also considered components of the adhesive. Although these raw materials are volatile, they are at least partially reacted during the preparation of the PUF resin.

[0189] Adhesive Solids – Definition and Procedure (Comparison with Adhesive A)

[0190] The amount of adhesive present after curing is referred to as "adhesive solids."

[0191] A disc-shaped asbestos sample (5 cm in diameter and 1 cm in height) was cut from the asbestos and heat-treated at 590°C for at least 30 minutes to remove all organic matter. The solids of the adhesive mixture were measured by dispensing a sample (approximately 2 g) of the adhesive mixture onto a heat-treated asbestos disc in a tinfoil container (see below for a mixing example). The tinfoil container containing the asbestos disc was weighed before and immediately after the addition of the adhesive mixture. Two such asbestos discs loaded with adhesive mixture were prepared in the tinfoil container and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the sample was weighed and the adhesive solids were calculated based on the average of the two results.

[0192] Preparation of composite strips (comparative adhesive A)

[0193] As described in the following examples, a 17.5% adhesive solid solution was obtained. At room temperature, a sample of the adhesive solution (70.1 g) was added to the pellets (460.0 g) in a mixing bowl. The resulting mixture was then mixed using a blender for approximately 2-5 minutes. The resulting mixture was then filled into 16 slots of a heat-resistant silicone template for the manufacture of strips. In the manufacture of each composite strip, the mixture placed in the slots was squeezed as needed and then smoothed with a plastic scraper to produce a uniform strip surface. The strip made using contrast adhesive A was cured for 1 hour at 200°C. After cooling to room temperature, the composite strip was stored in a climate chamber at 22°C / 50%rh.

[0194] Preparation of composite strips (comparative adhesive B)

[0195] As described in the following examples, a 25% adhesive component solid mixture is obtained. A sample (49.1 g) of the adhesive mixture is added to a pellet (460.0 g) preheated to 50° C. in a mixing bowl, which is also heated to 50° C. The mixture is then mixed using a mixer for approximately 2-5 minutes while the mixing bowl is still heated to 50° C. The resulting mixture is then filled into 16 narrow slots in a heat-resistant silicone template for making strips. In the manufacturing process of each composite strip, the mixture placed in the narrow slots is squeezed as needed, and then smoothed with a plastic scraper to produce a uniform strip surface. The strip made using contrast adhesive B was cured for 1 hour at 175° C. After cooling to room temperature, the composite strip was stored in a climate chamber at 22° C. / 50% rh.

[0196] Production of composite strips (adhesive composition according to the invention)

[0197] As described in the following examples, a 20% adhesive mixture (for adhesive mixtures having a ratio of Comparative Adhesive A: Comparative Adhesive B of 90:10, 75:25, or 50:50) or a 25% adhesive mixture (for adhesive mixtures having a ratio of Comparative Adhesive A: Comparative Adhesive B of 25:75 or 10:90) was obtained. Samples of the adhesive mixture (20% adhesive mixture, 61.3 g; 25% adhesive mixture, 49.1 g) were added to pellets (460.0 g) preheated to 50°C in a mixing bowl, which was also heated to 50°C. The resulting mixture was then mixed using a mixer for approximately 2-5 minutes while the mixing bowl was still heated to 50°C. The resulting mixture was then filled into 16 slots in a heat-resistant silicone template used to make the strips. During the manufacture of each composite strip, the mixture placed in the slots was squeezed as needed and then smoothed with a plastic spatula to produce a uniform strip surface. Strips made with adhesive mixtures of comparative adhesive A: comparative adhesive B in a ratio of 90:10 or 75:25 were cured at 200°C for 1 hour, while strips made with adhesive mixtures of comparative adhesive A: comparative adhesive B in a ratio of 25:75 or 10:90 were cured at 175°C for 1 hour. Strips made with an adhesive mixture of comparative adhesive A: comparative adhesive B in a ratio of 50:50 were cured at 175°C for 1 hour or at 200°C for 1 hour. After cooling to room temperature, the composite strips were stored in a climate chamber at 22°C / 50% rh.

[0198] Aging treatment of composite strips

[0199] The composite strips were aged by autoclaving (15 min / 120°C / 1.2 bar) or waterbath (3 h / 80°C) the strips and then cooling to room temperature. After initial drying for one day under ambient conditions, the composite strips were stored in a climate chamber at 22°C / 50% rh.

[0200] Measurement of mechanical strength of composite strips

[0201] The maximum load required to break the composite strip in a three-point bending test was recorded. For each data point, the average value was calculated based on four identically treated strips. Prior to measuring the maximum load, the composite strips were stored in a climate chamber at 22°C / 50% RH for at least three days.

[0202] Measurement of loss on ignition (LOI) of composite bars

[0203] The loss on ignition (LOI) of composite bars is measured in a small tinfoil container by treating them at 590°C. The tinfoil container is weighed and four bars (usually after breaking in a three-point bend test) are placed into the tinfoil container. The whole is weighed and then heat treated at 590°C for 30 minutes. After cooling to room temperature, the weight is recorded again and the loss on ignition (LOI) is calculated using the following formula:

[0204]

[0205] Binder Solubility – Definition

[0206] Binder solubility is defined as the difference between the loss on ignition (LOI) of the composite bar after aging in a water bath and the LOI of the composite bar before aging.

[0207] Water absorption measurement

[0208] The three strips were weighed and then placed in a beaker (565 mL, bottom top The water absorption of the adhesive was measured by immersing the strips in water (approximately 250 mL) for 24 hours in a beaker (height = 7.5 cm). The strips were rotated adjacent to each other at the bottom of the beaker so that the "top" was facing downward (i.e., the side with dimensions length = 5.6 cm and width = 2.5 cm). After a specified amount of time, the strips were lifted one by one and allowed to drip for one minute. The strips were held (gently) so that their long sides were almost vertical so that a drop of liquid dripped from one corner of the strip. The strips were then weighed and the water absorption was calculated using the following formula:

[0209]

[0210] Measurement of simulated spinning room emissions of ammonia and formaldehyde

[0211] Obtain 20% adhesive mixture in a manner similar to the program described in the following examples. When about to start each emission measurement, 700 μ L adhesive mixture is evenly distributed on the adhesive-free asbestos sample in a small ceramic crucible. By starting emission measurement in a baking oven heated to 95 ℃ a few minutes before inserting the sample, background ammonia and formaldehyde emissions are obtained. The sample is then loaded into a tube furnace and a temperature probe is inserted near the sample to measure the actual temperature. Then at 95 ℃, within the time of about 1 hour, the gas phase emission IR spectrum is recorded with a sampling frequency of 5 seconds. Each ammonia and formaldehyde concentration time series of the record obtained from the start of measurement to the disappearance of the water evaporation signal (usually about 30 minutes) is integrated to produce ammonia and formaldehyde emissions in the spinning chamber of the simulation. Each adhesive composition is measured three times, and the emission results are averaged. The result is provided in Table 1-1, Table 1-2 and Table 1-3 as a relative emission index compared with the comparison adhesive A1 (index 100).

[0212] Comparative adhesive compositions of the prior art

[0213] Comparative Adhesive A (phenolic resin modified with urea, PUF-phenolic resol), including Examples A1 and A2

[0214] A phenolic resin was prepared by reacting a 37% aqueous formaldehyde solution (606 g) with phenol (189 g) in the presence of a 46% aqueous potassium hydroxide solution (25.5 g) at a reaction temperature of 84° C. (previously heated at a heating rate of about 1° C. / min). The reaction was continued at 84° C. until the acid resistance of the resin was 4 and most of the phenol was converted. Urea (241 g) was then added and the mixture was cooled.

[0215] The acid resistance (AT) indicates how many times a given volume of adhesive can be diluted with acid without the mixture becoming turbid (adhesive precipitation). Sulfuric acid is used to determine the stopping criteria in adhesive production; an acid resistance below 4 indicates the end of the adhesive reaction. To measure the AT, a titrant is prepared by diluting 2.5 mL of concentrated sulfuric acid (>99%) with 1 L of ion-exchanged water. This titrant is then titrated with 5 mL of the adhesive under investigation at room temperature while manually shaking the adhesive to keep it in motion; if desired, a magnetic stirrer and magnetic bar can be used. The titration is continued until a slight turbidity appears in the adhesive that does not disappear when the adhesive is shaken.

[0216] Calculate the acid resistance (AT) by dividing the amount of titrating acid (mL) by the amount of sample (mL):

[0217] AT = (titration volume used (mL)) / (sample volume (mL))

[0218] Using the resulting urea-modified phenolic resin, an adhesive was prepared by adding a 28% aqueous ammonia solution (79.3 g for Comparative Adhesive A1 and 0 g for Comparative Adhesive A2) and ammonium sulfate (12.7 g), followed by water (729 g). The adhesive solids were then measured as described above, and the mixture was diluted with the required amount of water and 4% Momentive VS-142 silane (17.5-25% final adhesive solids solution, 0.2% adhesive solids silane).

[0219] Comparative Adhesive B (Protein-based Adhesive), Example B1

[0220] Mimosa tannin (11.0 g) was added to 0.5 M NaOH (38.5 g) stirred at room temperature. After further stirring at room temperature for 5-10 min, the resulting dark brown mixture (pH 9.0) was used for subsequent experiments.

[0221] A mixture of technical grade gelatin (28.0 g) in water (116.5 g for 20% adhesive component solids; 85.4 g for 25% adhesive component solids) was stirred at 50°C for approximately 15-30 minutes until all the gelatin was dissolved (pH 5.7). Firnis linseed oil (1.47 g) was then added, followed by a portion of the above-described Mimosa pudica extract mixture (6.30 g; thus effectively adding 1.40 g of tannin) and 4% silane (1.47 g, thus effectively adding 0.06 g of silane) (pH 6.8). 1 M NaOH (1.75 g) was then added (pH 7.3). After further stirring at 50° C. for 1-2 minutes, the resulting brown mixture was used in subsequent experiments.

[0222] Comparative Adhesive B (Protein-based Adhesive), Example B2

[0223] Mimosa tannin (11.0 g) was added to water (38.5 g) stirred at 50° C. After further stirring at 50° C. for 5-10 min, the resulting dark brown mixture (pH 4.2) was used for subsequent experiments.

[0224] A mixture of gluten protein (28.0 g) in water (117.4 g at 20% binder component solids) was stirred at room temperature for a few seconds before adding a portion of the above mimosa extract mixture (6.30 g; thus effectively 1.40 g tannins). Firnis linseed oil (1.47 g) was added followed by 4% silane (1.47 g, so effectively 0.06 g silane) (pH 5.9). After further stirring at room temperature for 5-10 minutes, the resulting light brown mixture was used in subsequent experiments.

[0225] Adhesive composition according to the present invention

[0226] General Adhesive Examples (adhesive mixtures having a ratio of Comparative Adhesive A: Comparative Adhesive B of 90:10, 75:25, or 50:50), Examples 1-3, 6, and 7-9

[0227] Comparative Adhesive B (20% adhesive component solids) was added to Comparative Adhesive A (20% adhesive solids) stirred at room temperature. The comparative adhesives were mixed in the desired ratio (A:B 90:10, 75:25, or 50:50) to form 60-120 g of the final adhesive mixture. After further stirring for 1-2 minutes, the resulting light to dark brown mixture (pH 8.0-9.6) was used in subsequent experiments.

[0228] Conventional Adhesive Examples (adhesive mixtures having a ratio of Comparative Adhesive A: Comparative Adhesive B of 25:75 or 10:90), Examples 4-5 and 10

[0229] Comparative Adhesive B (25% adhesive component solids) was added to Comparative Adhesive A (25% adhesive solids) stirred at room temperature. The comparative adhesives were mixed in the desired ratio (25:75 or 10:90) on a certain scale to form 60-120 g of the final adhesive mixture. After further stirring for 1-2 minutes, the resulting light to dark brown mixture (pH 7.8-9.0) was used for subsequent experiments.

[0230] The compositions of the comparative adhesives and the adhesives of the present invention and the results obtained by the testing procedures are shown below in Tables 1-1 to 1-3.

[0231] The results obtained for the adhesives of the present invention generally demonstrate very good performance. For example, the mechanical strength is impressive, especially after aging (e.g., Example 1). By using a dilution factor with a protein adhesive, ammonia emissions are reduced to a much higher degree, as expected, and formaldehyde is removed more efficiently (e.g., Example 1). Even small amounts of PUF adhesive significantly increase the solubility of the protein adhesive (e.g., Example 5). Excessive amounts of protein adhesive are not required to remove the majority of formaldehyde emissions resulting from the removal of ammonia from the PUF adhesive (e.g., Example 7).

[0232] Table 1-1: Adhesive compositions according to prior art

[0233] Examples A1 A2 B1 B2 Adhesive composition <![CDATA[Component a] > formaldehyde 32.0 33.0 - - phenol 27.0 27.8 - - potassium hydroxide 1.7 1.7 - - urea 34.4 35.5 - - ammonia 3.2 - - - ammonium sulfate 1.8 1.9 - - glucose syrup - - - - Ammonium sulfamate - - - - Hypophosphorous acid - - - - Industrial-grade gelatin - - 90.2 - gluten protein - - - 90.7 Mimosa Tannins - - 4.5 4.5 flaxseed oil - - 4.7 4.8 Sodium hydroxide - - 0.5 - <![CDATA[Other additives [b] > Silane 0.2 0.2 0.2 0.2 Adhesive mixing and strip manufacturing Adhesive solids (%) 17.5 17.5 - - Adhesive component solid content (%) - - 25.0 - pH value of the adhesive mixture 9.8 8.6 7.3 5.9 Curing temperature (℃) 200 200 175 - Bar Attributes Mechanical strength, unaged (kN) 0.62 0.66 0.63 - Mechanical strength, after AC aging treatment (kN) 0.29 0.28 0.50 - Mechanical strength, after WB aging treatment (kN) 0.33 0.37 0.33 - LOI, unaged (%) 2.56 2.56 2.49 - LOI, after autoclave aging (%) 2.71 2.52 2.54 - LOI, after water bath aging (%) 2.61 2.60 2.01 - Adhesive solubility (%) -2 -1 15 - Bar weight (g / bar) 24.9 25.9 25.9 - Water absorption, 24h (%) 7 7 20 - Simulating spinning chamber discharge Relative ammonia emission index 100 7 3 - Relative formaldehyde emission index 100 169 0 -

[0234] [a] Ingredient percentage. [b]Binder solids / binder component solids content (used in the tables for practical reasons, but additives are included in the definition of binder solids / binder component solids content).

[0235] Table 1-2: Adhesive mixtures obtained using comparative adhesive A1

[0236] Examples A1 1 2 3 4 5 B1 6 <![CDATA[Adhesive composition a] > A1 100 90 75 50 25 10 - 75 A2 - - - - - - - - <![CDATA[Adhesive composition b] > B1 - 10 25 50 75 90 100 - B2 - - - - - - - 25 Adhesive mixing and strip manufacturing Adhesive solids / component solids content (%) 17.5 20.0 20.0 20.0 25.0 25.0 25.0 20.0 pH value of the adhesive mixture 9.8 9.3 9.2 9.0 8.7 8.5 7.3 9.6 Curing temperature (℃) 200 200 200 200 175 175 175 200 Bar Attributes Mechanical strength, unaged (kN) 0.62 0.62 0.60 0.52 0.57 0.57 0.63 0.65 Mechanical strength, after AC aging treatment (kN) 0.29 0.39 0.42 0.31 0.42 0.37 0.50 0.30 Mechanical strength, after WB aging treatment (kN) 0.33 0.37 0.40 0.44 0.47 0.36 0.33 0.29 LOI, unaged (%) 2.56 2.57 2.45 2.52 2.51 2.54 2.49 2.50 LOI, after autoclave aging (%) 2.71 2.77 2.66 2.64 2.62 2.66 2.54 2.64 LOI, after water bath aging (%) 2.61 2.64 2.44 2.51 2.57 2.50 2.01 2.58 Adhesive solubility (%) -2 -3 0 0 -2 2 15 -3 Bar weight (g / bar) 24.9 27.0 25.7 26.9 27.4 26.4 25.9 27.1 Water absorption, 24h (%) 7 6 7 12 10 11 20 9 Simulating spinning chamber discharge Relative ammonia emission index 100 81 65 33 23 10 3 91 Relative formaldehyde emission index 100 66 17 17 10 0 0 41

[0237] [a] Based on adhesive solids. [b] Based on binder component solids content.

[0238] Table 1-3: Adhesive mixtures obtained using comparative adhesive A2

[0239] Examples A1 A2 7 8 9 10 B1 <![CDATA[Adhesive composition a] > A1 100 - - - - - - A2 - 100 75 50 50 25 - <![CDATA[Adhesive composition b] > B1 - - 25 50 50 75 100 B2 - - - - - - - Adhesive mixing and strip manufacturing Adhesive solids / component solids content (%) 17.5 17.5 20.0 20.0 20.0 25.0 25.0 pH value of the adhesive mixture 9.8 8.6 8.3 8.0 8.0 7.8 7.3 Curing temperature (℃) 200 200 200 200 175 175 175 Bar Attributes Mechanical strength, unaged (kN) 0.62 0.66 0.69 0.47 0.49 0.60 0.63 Mechanical strength, after AC aging treatment (kN) 0.29 0.28 0.53 0.46 0.35 0.43 0.50 Mechanical strength, after WB aging treatment (kN) 0.33 0.37 0.50 0.53 0.43 0.40 0.33 LOI, unaged (%) 2.56 2.56 2.46 2.51 2.58 2.63 2.49 LOI, after autoclave aging (%) 2.71 2.52 2.67 2.59 2.74 2.73 2.54 LOI, after water bath aging (%) 2.61 2.60 2.51 2.53 2.58 2.57 2.01 Adhesive solubility (%) -2 -1 -2 -1 0 2 15 Bar weight (g / bar) 24.9 25.9 27.2 26.8 26.9 26.8 25.9 Water absorption, 24h (%) 7 7 10 13 13 13 20 Simulating spinning chamber discharge Relative ammonia emission index 100 7 9 8 8 8 3 Relative formaldehyde emission index 100 169 62 24 24 10 0

[0240] [a] Based on adhesive solids. [b] Based on adhesive component solids content.

Claims

1. An aqueous adhesive composition, which is made from a mixture of the following substances: i) a phenol-urea-formaldehyde binder (PUF binder), and ii) a protein binder comprising at least one protein and at least one cross-linking agent selected from phenolic compounds.

2. The aqueous adhesive composition according to claim 1, wherein the PUF adhesive and the protein adhesive are mixed in a ratio such that the weight proportion B is in the range of 5 wt % to 95 wt % based on the total weight of A+B, wherein B is the weight of the adhesive component solids of the protein adhesive and A is the weight of the adhesive solids of the PUF adhesive. 3 . The aqueous adhesive composition according to claim 2 , wherein the weight proportion B is in the range of 10 wt % to 90 wt % based on the total weight of A+B.

4. The aqueous adhesive composition according to claim 2 or claim 3, wherein the weight proportion B is in the range of 5 wt % to 50 wt %, preferably 10 wt % to 45 wt %, more preferably 15 wt % to 40 wt %, based on the total weight of A+B, or wherein the weight proportion B is in the range of 50 wt % to 95 wt %, preferably 60 wt % to 90 wt %, more preferably 70 wt % to 90 wt %, based on the total weight of A+B.

5. The aqueous adhesive composition according to any one of the preceding claims, wherein the PUF adhesive is a phenol-urea-formaldehyde resole adhesive.

6. The aqueous adhesive composition according to any one of the preceding claims, wherein for the raw materials phenol, formaldehyde and urea used to prepare the PUF adhesive, the molar ratio of phenol to formaldehyde is 1:2.5 to 1:6; preferably 1:3 to 1:5, and / or The amount of urea is 20 to 60 wt%, preferably 30 to 50 wt%, based on the total weight of phenol, formaldehyde and urea.

7. The aqueous adhesive composition according to any one of the preceding claims, wherein the PUF adhesive is modified with ammonia or is not modified with ammonia, wherein the amount of ammonia is preferably 0 wt % to 6 wt %, more preferably 0 wt % to 4 wt %, more preferably 0 wt % to 3 wt %, based on the total weight of the raw materials phenol, formaldehyde and urea used to prepare the PUF adhesive, wherein the PUF adhesive is preferably not modified with ammonia.

8. The aqueous adhesive composition according to claim 1 , wherein the at least one protein is selected from the group consisting of proteins of animal origin, including collagen, gelatin, hydrolyzed gelatin and proteins from milk (casein, whey), eggs; proteins from jellyfish, proteins produced by recombinant technology; proteins from insects such as silkworms, such as sericin; proteins of plant origin, including gluten, proteins from algae, legumes, cereals, whole grains, nuts, seeds and fruits, such as proteins from buckwheat, oats, rye, millet, maize (corn), rice, wheat, bulgur, sorghum, amaranth, quinoa, soybeans (soy protein), lentils, kidney beans, white beans, mung beans, chickpeas, cowpeas, lima beans, pigeon peas, lupines, winged beans, almonds, Brazil nuts, cashews, pecans, walnuts, rapeseed, cottonseed, pumpkin seeds, sesame seeds and sunflower seeds, proteins produced by recombinant technology; mussel foot protein or a combination thereof.

9. The aqueous adhesive composition according to any one of the preceding claims, wherein the adhesive composition comprises at least two proteins, wherein one protein is at least one selected from the group consisting of proteins of animal origin: including collagen, gelatin, hydrolyzed gelatin and proteins from milk (casein, whey), eggs; proteins from jellyfish, proteins produced by recombinant technology; proteins from insects such as silkworms, such as sericin, such as mussel foot protein; and the other protein is at least one selected from the group consisting of proteins of plant origin. Proteins: This group includes gluten, proteins from algae, legumes, cereals, whole grains, nuts, seeds, and fruits, such as proteins from buckwheat, oats, rye, millet, maize (corn), rice, wheat, bulgur wheat, sorghum, amaranth, quinoa, soybeans (soy protein), lentils, kidney beans, white beans, mung beans, chickpeas, cowpeas, lima beans, pigeon peas, lupine, winged beans, almonds, Brazil nuts, cashews, pecans, walnuts, rapeseed, cottonseed, pumpkin seeds, sesame seeds, and sunflower seeds, and proteins produced through recombinant technology.

10. The aqueous adhesive composition according to any one of the preceding claims, wherein the at least one phenolic compound is selected from the group consisting of simple phenolic compounds such as hydroxybenzoic acid, hydroxybenzaldehyde, hydroxyacetophenone, hydroxyphenylacetic acid, cinnamic acid, cinnamate, cinnamaldehyde and cinnamyl alcohol; coumarins such as isocoumarins; chromones; flavonoids; chalcones such as dihydrochalcones; aurone; flavanones such as flavanols; flavans; leucocyanidins; flavan-3-ols; flavones; anthocyanidins; deoxyanthocyanidins; anthocyanin; biflavonoids; benzophenone ; Xanthan gum; stilbene; betalain; polyphenols and / or polyhydroxyphenols, such as lignans, neolignans (dimers or oligomers obtained by coupling lignin monomers such as p-coumarol, coniferyl alcohol and sinapyl alcohol), lignins (mainly synthesized from lignin monomer precursors p-coumarol, coniferyl alcohol and sinapyl alcohol), tannins, such as tannates (salts of tannins), condensed tannins (proanthocyanidins), hydrolyzed tannins, gallic tannins, ellagitannins, complex tannins, tannic acid, tannic anhydride, such as brown algae polyphenols; compounds containing sulfonated phenols and combinations thereof.

11. The aqueous adhesive composition according to any one of the preceding claims, wherein the at least one protein comprises or is gelatin, gluten or a combination thereof, and / or wherein the at least one phenolic compound comprises or is tannin, wherein the tannin is preferably selected from one or more of the group consisting of tannic acid, condensed tannins (proanthocyanidins), sulfonated tannins, hydrolyzed tannins, gallic tannins, ellagitannins, complex tannins and / or tannins derived from one or more of oak, chestnut, staghorn sumac, fringed cup grass, sackwood, acacia, mimosa, black wattle bark, grape, gallnut, black tea, terminalia chebula, caesalpinia spinulosa, oak and eucalyptus.

12. The aqueous adhesive composition according to any one of the preceding claims, wherein the content of the at least one phenolic compound, in particular tannin, is in the range of 1 to 30 wt.-%, more preferably 2 to 15 wt.-%, most preferably 3 to 10 wt.-%, based on the dry weight of the at least one protein.

13. The aqueous adhesive composition according to any one of the preceding claims, wherein the total amount of PUF binder, the at least one protein and the at least one cross-linking agent selected from phenolic compounds in the aqueous adhesive composition is in the range of 75 wt % to 100 wt %, preferably 85 wt % to 97 wt %, based on the total weight of the binder solids of the PUF binder and the binder component solids of the protein binder.

14. The aqueous binder composition according to any one of the preceding claims, wherein the protein binder further comprises at least one glycerol fatty acid ester, wherein the content of the glycerol fatty acid ester is preferably 0.6 to 30 wt. %, more preferably 2 to 10 wt. %, more preferably 3 to 7.5 wt. %, based on the dry weight of the at least one protein and the at least one phenolic compound.

15. A method of producing a mineral fibre product comprising the steps of contacting mineral fibres with an aqueous binder composition according to any one of claims 1 to 14 and curing the binder.

16. A method for producing a mineral fiber product according to claim 15, wherein the method comprises the following steps: - manufacture of melts of raw materials, - fiberizing the melt to form mineral fibers by means of a fiber-forming device, wherein the formed mineral fibers are preferably introduced into a spinning chamber, - providing said mineral fibers in the form of a collected web, - applying the aqueous binder composition to the mineral fibers before, during or after providing the collected web to form a mixture of mineral fibers and binder composition, wherein the aqueous binder composition is preferably applied by spraying in the spinning chamber, preferably before providing the collected web, - curing the binder composition mixed with the mineral fibers.

17. A method for producing a mineral fiber product according to claim 13 or 14, wherein the curing is carried out at a temperature of 15 to 250°C, preferably 150 to 250°C, more preferably 175 to 225°C.

18. A mineral fiber product comprising mineral fibers bonded by a binder obtained by curing an aqueous binder composition according to any one of claims 1 to 14, preferably obtained by a process according to any one of claims 15 to 17.

19. Use of a protein binder comprising at least one protein and at least one crosslinking agent selected from phenolic compounds in a phenol-urea-formaldehyde binder (PUF binder) for reducing at least one of formaldehyde emissions and ammonia emissions during application of the obtained aqueous binder composition to mineral fibers in a spinning chamber, compared to application of the PUF binder without the addition of a protein binder to mineral fibers in a spinning chamber, wherein the use is preferably carried out in a method according to any one of claims 15 to 17.

20. Use of a phenol-urea-formaldehyde binder (PUF binder) in a protein binder comprising a combination of at least one protein and at least one crosslinking agent selected from phenolic compounds for reducing the water absorption of a mineral fiber product produced from the obtained aqueous binder composition and mineral fibers compared to the water absorption of a mineral fiber product produced from the protein binder without the addition of the PUF binder, wherein the use is preferably carried out in a method according to any one of claims 15 to 17.

21. Use of the aqueous binder composition according to any one of claims 1 to 14 for producing mineral fiber products.

22. A method for reducing formaldehyde emissions and / or ammonia emissions during application of a phenol-urea-formaldehyde binder (PUF binder) to mineral fibers in a spinning chamber, the method comprising the following steps: A protein binder comprising at least one protein and at least one cross-linking agent selected from phenolic compounds is added to the PUF binder and the obtained aqueous binder composition is applied to mineral fibers instead of the PUF binder in a spinning chamber, wherein the method is preferably according to any one of claims 15 to 17.

23. A method of reducing the water absorption of a mineral fiber product bonded with a cured protein binder comprising a combination of at least one protein and at least one cross-linking agent selected from phenolic compounds, the method comprising the steps of: adding a phenol-urea-formaldehyde binder (PUF binder) to the protein binder and applying the obtained aqueous binder composition to mineral fibers instead of the protein binder and curing the applied binder to obtain a mineral fiber product, wherein the process is preferably according to any one of claims 15 to 17.

Images