RU2794599C1 - Binder for mineral wool - Google Patents

Abstract

FIELD: chemical industry.

SUBSTANCE: binder composition for mineral fibers, a mineral wool product and a method for its manufacture, the use of the composition and the compounds included in it. The formaldehyde-free binder composition for mineral fibers contains one or more phenol-containing compounds, at least one protein, one or more compounds containing the divalent metal cation M²⁺, at least one compound containing the monovalent metal cation M⁺.

EFFECT: composition for binding mineral fibers that does not require high temperature for curing and improves the properties of products from renewable relatively harmless and non-corrosive materials, and the creation of a mineral wool product.

20 cl, 1 dwg, 8 tbl, 25 ex

Description

The field of technology to which the invention belongs

The present invention relates to a mineral fiber binder composition, to a method for making a mineral wool product using a binder composition, to a mineral wool product made using a binder composition, to the use of a binder composition, and to the use of at least one compound containing the divalent metal cation M ²⁺ , as well as the use of at least one compound containing the divalent metal cation M ²⁺ and at least one compound containing the monovalent metal cation M ⁺ , respectively, in the binder composition.

State of the art

Mineral fiber products typically contain man-made vitreous fibers (VFIs), such as, for example, glass fibre, ceramic fibre, basalt fibre, slag wool, mineral wool and rock wool (stone wool), which are bonded together by a cured thermoset polymer binder. material. For use as heat or sound insulating materials, mats of bonded mineral fiber are usually made by converting a melt obtained from suitable raw materials into fibers in a conventional manner, for example, by means of the spinning cup process or the cascaded rotor process. The fibers are blown into the forming chamber and, while they are in the air and hot, they are sprayed with a binder solution and randomly deposited in the form of a mat or web on a moving conveyor. The fiber mat is then transferred to a curing oven where heated air is blown through the mat to cure the binder and firmly bond the mineral fibers to each other.

In the past, the preferred binder resins have been phenol-formaldehyde resins, which can be economically made and which can be diluted with urea before being used as a binder. However, current and proposed legislation aimed at reducing or eliminating formaldehyde emissions has led to the development of formaldehyde-free binders, such as, for example, binder compositions based on polycarboxypolymers and polyols or polyamines, which are disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, US-A-5,318,990 and US-A-2007/0173588.

Another group of non-phenol-formaldehyde binders are the products of the reaction of addition/elimination (elimination) of aliphatic and/or aromatic anhydrides with alkanolamines, for example, the products described in documents 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 have excellent bonding properties in terms of cure rate and cure density. WO 2008/023032 discloses urea-modified binders of this type which provide mineral wool products having reduced moisture absorption.

Because some of the raw materials used in the manufacture of these binders are quite expensive chemicals, there is a continuing need to make formaldehyde-free binders that are economical.

An additional effect associated with previously known aqueous mineral fiber binder compositions is that at least most of the raw materials used to make these binders are derived from fossil fuels. There is a continuing consumer trend towards products that are wholly or at least partially made from renewable materials, and therefore there is a need to produce mineral wool binders that are at least partially made from renewable materials.

An additional effect associated with previously known aqueous mineral fiber binder compositions is that they include components that are corrosive and/or harmful. This requires protective measures for equipment involved in the manufacture of mineral wool products to prevent corrosion, and also requires safety measures for persons working with this equipment. This leads to increased costs and health problems, and therefore there is a need to provide mineral fiber binder compositions with a reduced content of corrosive and/or harmful materials.

Another side effect associated with previously known aqueous mineral fiber binder compositions is that these binders are commonly associated with heavy binder curing equipment. The curing equipment is typically an oven operating at temperatures well above 100°C, eg around 200°C. The length of the oven is several meters to accommodate the web that is continuously fed into the oven and to ensure that the web is fully cured as it exits the oven. Such furnace equipment is associated with high energy costs.

In the recent past, binder compositions have been proposed that are largely made from renewable materials and are not corrosive and/or harmful.

However, there is still a need to provide binder compositions that are made to a large extent from a renewable material and that are not corrosive and/or harmful, while at the same time showing improved properties of mineral wool products made from such binders. .

Reference C. Peña, K. de la Caba, A. Eceiza, R. Ruseckaite, I. Mondragon in Biores. Technol. 2010, 101, 6836-6842 concerns the replacement of non-biodegradable plastic films with renewable raw materials from plants and meat industry waste. In this regard, this reference describes the use of hydrolysable chestnut tree tannin to modify gelatin to form films. The reference does not describe binders, in particular it does not describe binders for mineral wool.

Brief summary of the invention

Accordingly, the aim of the present invention was to provide a binder composition that is particularly suitable for bonding mineral fibers, uses renewable materials as raw materials, reduces or eliminates the use of corrosive and/or harmful materials, and at the same time improves the properties of products made from them. mineral products.

In addition, the aim of the present invention was to provide a binder composition that does not require high temperature for curing and, therefore, eliminates the need for high temperature in the manufacture of an article bonded with a binder composition, and at the same time improves the properties of products made from mineral wool. products.

Another object of the present invention was to provide a mineral wool product bonded with such a binder composition.

Another object of the present invention was to provide a method for manufacturing such a mineral wool product.

Another object of the present invention was to use such a binder composition for the manufacture of a mineral wool product.

Another object of the present invention was to improve the properties, in particular with regard to water absorption and/or mechanical properties and/or aging properties of a mineral wool product containing mineral fibers bonded together with a binder, and the binder composition obtained as a result of curing, containing at least one phenol-containing compound and at least one protein.

According to a first aspect of the present invention, there is provided a preferably formaldehyde-free mineral fiber binder composition comprising:

- at least one phenol-containing compound,

- at least one protein,

- a compound containing at least one divalent metal cation M ²⁺ .

According to a second aspect of the present invention, there is provided a mineral wool product comprising mineral fibers bonded together with a binder and obtained by curing such a binder composition.

In accordance with a third aspect of the present invention, there is provided a process for making a mineral wool product, which includes the steps of contacting mineral fibers with such a binder composition.

According to a fourth aspect of the present invention, the use of such a binder composition for the manufacture of a mineral wool product is provided.

According to a fifth aspect of the present invention, there is provided the use of at least one compound containing the divalent metal cation M ²⁺ in a mineral fiber binder composition comprising at least one phenol-containing compound and at least one protein to improve water absorption and/ or the mechanical and/or aging properties of a mineral wool product containing mineral fibers bonded together with a binder and a cured binder composition.

According to a sixth aspect of the present invention, there is provided the use of at least one compound containing the divalent metal cation M ²⁺ and at least one compound containing the monovalent metal cation M ⁺ , in a formaldehyde-free mineral fiber binder composition containing at least one phenol-containing compound and at least one protein, for improving water absorption and/or mechanical properties and/or aging properties of a mineral wool product containing mineral fibers bonded together with a binder and a cured binder composition .

The present inventors have surprisingly found that it is possible to make a mineral wool product containing mineral fibers bonded together with a binder and obtained by curing the binder composition, wherein the binder composition can be made largely from renewable materials without contains or contains only to a small extent any corrosive and/or harmful substances, and the manufacture of a mineral wool product does not lead to contamination, for example, by compounds such as VOCs (Volatile Organic Compounds) during manufacture, and at the same time such a product shows improved properties, in particular with regard to water absorption and/or mechanical properties and/or aging properties.

Description of the figure

The results of the experimental work described above are summarized in FIG. 1, where

короткая пунктирная линия) и NaOH (×, точечная линия);Fig. 1 (A), (B) and (C) shows: mechanical strength of composite bars made from stone granules and IMAGEL® LA, modified with chestnut tannin in the presence of Ca(OH) ₂ , not aged (A), aged in autoclave (B) and aged in a water bath (C) (■, solid line), Ca:Na 60:40 (●, long dotted line), Ca:Na 33:67 (▲, dotted line), Ca:Na 14: 86 (

short dotted line) and NaOH (×, dotted line);

in Fig 1 (D): the degree of solubility of the binder, calculated as the loss of the content of the binder due to aging in a water bath (D);

1 (E), (F): water absorption of the composite bars measured after 3 hours (E) and 24 hours (F) in water.

Implementation of the invention

The binder composition according to the present invention includes:

- at least one phenol-containing compound,

- at least one protein,

- a compound containing at least one divalent metal cation M ²⁺ .

In a preferred embodiment, the binder in accordance with the present invention does not contain formaldehyde.

For the purposes of this application, the term "formaldehyde-free" is used to describe a mineral wool product in which the formaldehyde emission from the mineral wool product is less than 5 µg/m ² /h, preferably less than 3 µg/m ² /h. Preferably, the test is carried out in accordance with the ISO 16000 standard for aldehyde emission control.

An unexpected advantage of the embodiments of mineral wool products in accordance with the present invention is that they exhibit self-healing properties. After exposure to very harsh conditions, where the mineral wool products lose some of their strength, the mineral wool products according to the present invention can partially regain their original strength. This is different from traditional mineral wool products where the loss of strength after exposure to harsh environmental conditions is irreversible. Without wishing to be bound by any particular theory, the present inventors believe that this unexpected property of the mineral wool products of the present invention is due to the complex nature of the bonds formed in the phenol-containing compound cross-linked protein network, which also includes quaternary structures and hydrogen bonds, which allows the formation of bonds in the network after returning to normal environmental conditions. For an insulating product that can be exposed to very high temperatures in summer, for example, as a roof insulation, this is an important advantage for long-term stability of the product.

A compound containing a divalent metal cation

The present inventors have unexpectedly found that the properties of a mineral wool product obtained using a binder containing at least one phenol-containing compound and at least one protein can be significantly improved by adding at least one compound containing a divalent metal cation M ^{2 +} , to the binder composition.

In particular, the water absorption properties and/or the mechanical properties and/or the aging properties of the mineral wool product can be significantly improved.

In one embodiment, the compound containing at least one divalent metal cation M ²⁺ contains at least one divalent metal cation M ²⁺ from the alkaline earth metals, Mn, Fe, Cu, Zn, Sn.

In one embodiment, the compound containing at least one divalent metal cation M ²⁺ is an ionic compound, in particular a salt containing a divalent metal cation M ²⁺ , in particular alkaline earth metals, Mn, Fe, Cu, Zn, Sn or mixtures thereof, and one or more counterions in the form of anions.

In one embodiment, the compound containing the divalent metal cation M ²⁺ includes one or more compounds selected from the group M(OH) ₂ , MO, M(HCO ₃ ) ₂ , MCO ₃ , M(H ₂ PO ₄ ) ₂ , MHPO ₄ , M ₃ (PO ₄ ) ₂ , M(HPO ₃ ), M(H ₂ PO ₂ ) ₂ , MSO ₄ , MCl ₂ , MHNSO ₃ , in particular M(OH) ₂ .

In one embodiment, the compound containing the divalent metal cation M ²⁺ includes one or more compounds selected from M(ClO ₃ ) ₂ and M(ClO ₄ ) ₂ .

In one embodiment, the compound containing the divalent metal cation M ²⁺ includes Ca ²⁺ .

In an alternative embodiment, the compound containing the divalent metal cation includes Mn ²⁺ , Fe ²⁺ , Cu ²⁺ , Zn ²⁺ , Sn ²⁺ , Ba ²⁺ , Nd ²⁺ , or mixtures thereof.

In one embodiment, the binder composition contains at least one divalent metal cation compound in an amount of 0.1 wt. % up to 10 wt. %, for example, from 0.2 wt. % up to 8 wt. %, for example, from 0.3 wt. % up to 5 wt. %, for example, from 0.4 wt. % to 4.3 wt. %, for example, from 1.0 wt. % to 4.3 wt. %, based on the total dry weight of the phenol-containing compound and protein.

In one embodiment, the binder composition further comprises at least one monovalent metal cation-containing compound M ⁺ , in particular in the form of at least one monovalent metal cation from the alkali metal-containing compound.

The present inventors have surprisingly found that by adding both a compound containing a divalent metal cation M ²⁺ and a compound containing a monovalent metal cation M ⁺ , particularly good properties of mineral wool products made with the binder composition can be achieved and that in particular, the properties of mineral wool products made using such a binder composition can be adapted depending on the requirements for such a mineral wool product.

In one embodiment, the binder composition contains at least one monovalent metal cation M+ in the form of at least one alkali metal cation.

In one embodiment, the binder composition contains at least one monovalent metal cation in the form of a monovalent metal cation of Li, Na, K, in particular Na.

In one embodiment, the binder composition contains at least one compound containing a monovalent metal cation M ⁺ in an amount of 0.01 wt. % up to 6 wt. %, for example, from 0.1 wt. % up to 5 wt. %, for example, 0.2 wt. % % up to 4 wt. %, for example, from 0.3 wt. % to 3.3 wt. %, for example, from 0.3 wt. % up to 2.0 wt. %, based on the total dry weight of the phenol-containing compound and protein.

The inventors of the present invention surprisingly found that by adjusting the ratio of the compound containing the divalent metal cation M ²⁺ to the compound containing the monovalent metal cation M ⁺ in the binder compositions, it is possible to achieve certain characteristics in the properties of the mineral wool product obtained from the binder compositions. .

In one embodiment, the binder composition contains at least one compound containing a divalent metal cation M ²⁺ and at least one compound containing a monovalent metal cation M ⁺ , and where the molar ratio of the divalent metal cation to the monovalent metal cation is in the range 10:90 to 90:10, e.g. 14.3:85.7 to 90:10, e.g. 14.3:85.7 to 60:40, e.g. 20:80 to 80:20, eg 25:75 to 75:25, eg 33.3:66.7 to 60:40, eg 40:60 to 60:40, eg 50:50.

Phenol-containing binder compound

The binder composition according to the present invention comprises a phenol-containing binder compound, in particular one or more phenolic compounds.

Phenolic compounds, or phenols, are compounds that have one or more hydroxyl groups attached directly to the aromatic ring. Polyphenols (or polyhydroxyphenols) are compounds that have more than one phenolic hydroxyl group attached to one or more aromatic rings. Phenolic compounds are characteristic of plants, and as a group they usually occur as esters or glycosides rather than as free compounds.

The term phenols covers a very large and diverse group of chemical compounds. Preferably, the phenol-containing compound is a compound according to the scheme based on the number of carbon atoms in the molecule, as detailed by W. Vermerris, R. Nicholson, in Phenolic Compound Biochemistry, Springer Netherlands, 2008.

In one embodiment, the phenol-containing compound includes a phenol-containing compound such as simple phenols such as hydroxybenzoic acids such as hydroxybenzoic aldehydes such as hydroxyacetophenones such as hydroxyphenylacetic acids such as cinnamic acids such as cinnamic acid esters such as cinnamic aldehydes such as cinnamic alcohols such as coumarins such as isocoumarins such as chromones such as flavonoids such as chalcones such as dihydrochalcones such as aurones such as flavanones such as flavanonols such as flavans such as leucoanthocyanidins, such as flavan-3-ols such as flavones such as anthocyanidins such as deoxyanthocyanidins such as anthocyanins such as biflavonyls such as benzophenones such as xanthones such as stilbenes such as betacyanins such as polyphenols and/or polyhydroxyphenols such as lignans, neolignans (dimers or oligomers resulting from the binding of monolignols such as p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol), such as lignins (synthesized mainly from monolignol precursors p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol ), such as tannins, such as tannates (salts of tannins), such as condensed tannins (proanthocyanidins), such as hydrolysable tannins, such as gallotannins, such as ellagitannins, such as complex tannins, such as tannic acid, such as flobabens, such like phlorotannins.

In one embodiment, the phenol-containing compound is selected from the group consisting of simple phenols, phenol-containing compounds with a structure more complex than C6, such as simple phenol oligomers, polyphenols and/or polyhydroxyphenols.

The phenol-containing compounds according to the present invention may also be synthetic or semi-synthetic molecules or constructs containing phenols, polyphenols. An example of such a construct is a protein, peptide, peptoids (such as linear and/or cyclic oligomers and/or polymers of N-substituted glycines, N-substituted β-alanines) or arylopeptoids (such as linear and/or cyclic oligomers and/or polymers of N -substituted aminomethylbenzamides) modified with phenol-containing side chains. Another example is a phenol-decorated dendrimer containing side chains.

In one embodiment, the phenol-containing compound of the present invention is a quinone. Quinones are oxidized derivatives of aromatic compounds and are often easily prepared from reactive aromatic compounds with electron-donating substituents, such as phenols. Quinones suitable for the present invention include benzoquinones, naphthoquinone, anthraquinone and lawson.

Tannins are a group of compounds with a wide variety of structures that share the ability to bind and precipitate proteins. Tannins are found in abundance in many different plant species, such as oak, chestnut, staghorn sumac, and tellima grandiflora. Tannins can be present in leaves, bark and fruits. Tannins can be divided into three groups: condensed tannins, hydrolysable tannins and complex tannins. Condensed tannins, or proanthocyanidins, are oligomeric or polymeric flavonoids composed of flavan-3-ol (catechin) units. Gallotannins are hydrolyzable tannins with a polyol core substituted with 10-12 gallic acid residues. The most common polyol in gallotannins is D-glucose, although some gallotannins contain catechin and triterpenoid units as the main polyol. Ellagitannins are hydrolysable tannins that differ from gallotannins in that they contain additional C-C bonds between adjacent haloyl moieties. Complex tannins are defined as tannins in which a catechin unit is glycosidically bonded to either a gallotannin or an ellagitannin unit.

In one embodiment, the tannin is selected from one or more of the group consisting of tannic acid, condensed tannins (proanthocyanidins), hydrolysable tannins, gallotannins, ellagitannins, complex tannins, and/or tannin derived from one or more species of oak, chestnut, sumac. deer-horned, tellima grandiflora, quebracho, acacia, mimosa, black locust bark, grapes, gall, gambir, myrobalan, edible taro, wallonia and eucalyptus.

The inventors have found that a wide variety of such phenol-containing compounds can be used to cross-link proteins to form a binder composition. Often, these phenol-containing compounds are derived from plant tissues and are therefore a renewable material. In some embodiments, the compounds are also non-toxic and non-corrosive. An additional advantage is that these compounds are antimicrobial and therefore impart their antimicrobial properties to the mineral wool product bound by such a binder.

Protein component of the binder

Preferably the protein component of the binder is selected from the group consisting of proteins of animal origin, including collagen, gelatin, hydrolysed gelatin and milk protein (casein, whey), eggs; jellyfish proteins, proteins obtained by recombinant methods; insect proteins such as silkworms such as sericin; proteins from plant sources, including proteins from algae, legumes, cereals, whole grains, nuts, seeds and fruits, such as protein 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, lupins, kidney beans, almonds, Brazil nuts, cashews, pecans, walnuts, canola seeds, cotton seeds, pumpkin seeds, hemp seeds, sesame seeds and sunflower seeds; polyphenolic proteins such as mussel foot protein.

Collagen is a very common material in living tissues. It is the main component of connective tissue and makes up 25-35% of the total protein content in mammals. Gelatin is obtained by chemical decomposition of collagen. Gelatin can also be obtained by recombinant methods. Gelatin is water soluble and has a molecular weight of 10,000 to 500,000 g/mol, eg 30,000 to 300,000 g/mol, depending on the degree of hydrolysis. Gelatin is a widely used food product, and therefore it is generally accepted that this compound is completely non-toxic and no precautions are required when working with gelatin.

Gelatin is a heterogeneous mixture of single or multi-chain polypeptides, usually showing helical structures. In particular, the triple helix of type I collagen derived from skin and bone, which is the source of gelatin, consists of two α1(I) and one α2(I) chains.

Coil-spiral transformations can occur in gelatin solutions.

Type A gelatins are obtained by acid treatment. Type B gelatins are obtained by treatment with a base.

Chemical cross-links can be introduced into gelatin. In one embodiment, a transglutaminase is used to bind lysine to glutamine residues; in one embodiment, glutaraldehyde is used to link lysine to lysine; in one embodiment, tannins are used to bind lysine residues.

Gelatin can also be further hydrolyzed to smaller fragments up to 3000 g/mol.

When the gelatin solution is cooled, collagen-like coils can form. Gelatin can form helical structures.

In one embodiment, a cured binder containing a protein having helical structures.

In one embodiment, at least one protein is a low strength gelatin, for example, gelatin having a gel strength of 30 to 125 Bloom.

In one embodiment, at least one protein is a medium strength gelatin, for example, gelatin having a gel strength of 125 to 180 Bloom.

In one embodiment, the at least one protein is a high strength gelatin, such as gelatin having a gel strength of 180 to 300 Bloom.

In a preferred embodiment, the gelatin is preferably obtained from one or more sources from the group consisting of mammalian species, birds such as cow, pig, horse, poultry, and/or fish scales, skins.

In one embodiment, urea may be added to the binder composition of the present invention. The inventors have found that the addition of even small amounts of urea leads to gelatin denaturation, which can slow down gelation, which may be desirable in some embodiments. The addition of urea may also lead to softening of the product.

The inventors have found that the carboxylic acid groups in gelatins interact effectively with tri- and tetravalent ions, such as aluminum salts. This is especially true for type B gelatins, which contain more carboxylic acid groups than type A gelatins.

The present inventors have found that, in some embodiments, curing/drying of binder compositions of the present invention that contain gelatin should not be started at very high temperatures.

The inventors have found that starting the cure at low temperatures can result in stronger products. While not wishing to be bound by any particular theory, the inventors speculate that starting cure at high temperatures may result in an impermeable outer shell of the binder composition that makes it difficult for water to escape underneath.

Surprisingly, it has been found that binders in accordance with the present invention containing gelatins have a very high heat resistance. The authors of the present invention have found that in some embodiments, the implementation of the cured binder can withstand temperatures up to 300°C without decomposition.

Reaction of binder components

Without wishing to be bound by any particular theory, the present inventors believe that the reaction between a phenol-containing compound and a protein depends at least in part on the oxidation of phenols to quinones, followed by nucleophilic attack on the amino and/or thiol groups of the protein, resulting in protein crosslinking. phenolic compounds.

Without wishing to be bound by any particular theory, the inventors of the present invention believe that an improvement in the properties of mineral wool articles (products) made with binders in accordance with the present invention, due to the presence of a compound containing a divalent metal cation M ²⁺ , can be explained by the chelating effect, in which M ²⁺ crosslinks the negatively charged groups of the cured binder.

By providing at least one compound containing the divalent metal cation M ²⁺ and at least one compound containing the monovalent metal cation M ⁺ , this cross-linking effect can, according to the theory of the inventors, be modulated and the properties of mineral wool products can be changed by individual order.

In a preferred embodiment, the content of phenol-containing compounds in the composition of the binder in accordance with the present invention is from 1 to 70 wt. %, for example, from 2 to 60 wt. %, for example, from 3 to 50 wt. %, for example, from 4 to 40 wt. %, for example from 5 to 35 wt. %, calculated on a dry protein basis.

In an alternative preferred embodiment, the weight ratio of (lysine+cysteine) in protein to (phenol) in the phenol-containing compound is 1:5.78-1:0.08, such as 1:2.89-1:0.09, such as 1: 1.93 - 1:0.12, e.g. 1:1.45 - 1:0.15, e.g. 1:1.16 - 1:0.17.

The mass ratio of (lysine+cysteine) in protein to (phenol) in a phenol-containing compound should be understood as the ratio of the total mass of lysine+cysteine residues in the protein component to the total mass of phenol residues in the phenol-containing compound.

The inventors of the present invention have found that the curing of the binder is greatly accelerated under alkaline conditions. Therefore, in one embodiment, the mineral fiber binder composition contains a pH adjuster, preferably in the form of a base such as an organic base such as an amine or salts thereof, an inorganic base such as ammonia or salts thereof.

In a preferred embodiment, the binder composition according to the present invention has a pH greater than 7, such as greater than 8, such as greater than 9, such as in the range of above 7 to below 11.

In one embodiment, the protein includes polyphenolic proteins.

These proteins contain high levels of the post-translationally modified-oxidized form of tyrosine, L-3,4-dihydroxyphenylalanine (levodopa, L-DOPA). See also J.J. Wilker Nature Chem. Biol. 2011, 7, 579-580 for reference to these proteins.

Additives

In a preferred embodiment, the binder composition according to the present invention contains additives.

Said additives may be components such as one or more reactive or non-reactive silicones which may be added to the binder. Preferably, one or more reactive or non-reactive silicones are selected from the group consisting of a silicone consisting of a backbone that contains organosiloxane moieties, especially diphenylsiloxane moieties, alkylsiloxane moieties, preferably dimethylsiloxane moieties, bearing at least one hydroxyl, acyl, carboxyl or anhydride , amine, epoxy or vinyl functional group capable of reacting with at least one of the components of the binder composition, preferably present in an amount of 0.1-15 wt. %, preferably 0.1-10 wt. %, more preferably 0.3-8 wt. %, based on the total weight of the binder.

In one embodiment, an emulsified hydrocarbon oil may be added to the binder.

As already described above, many phenol-containing compounds, in particular polyphenols, have antimicrobial properties and therefore impart antimicrobial properties to the binder. However, in one embodiment, an antifouling agent may be added to the binder compositions.

In one embodiment, an anti-swelling agent such as tannic acid and/or tannins may be added to the binder.

In one embodiment, the binder composition in accordance with the present invention contains additives in the form of amine linkers and/or thiol/thiolate linkers. Said additives in the form of amine linkers and/or thiol/thiolate linkers are particularly useful when the crosslinking reaction of the binder proceeds via the quinone-amine and/or quinone-thiol pathway.

In one embodiment, the binder compositions of the present invention contain additional additives in the form of additives selected from the group consisting of PEG type reagents, silanes, fatty acid esters of glycerol, and hydroxyapatites.

Oxidizers as additives may be intended to increase the rate of oxidation of phenols. One example is the enzyme tyrosinase, which oxidizes phenols to hydroxyphenols/quinones and therefore speeds up the binder formation reaction.

In another embodiment, the oxidizing agent is oxygen, which is supplied to the binder.

In one embodiment, curing is carried out in an oxygen-enriched environment.

A mineral wool product containing mineral wool fibers bonded together with a binder.

The present invention also relates to a mineral wool product bonded using a binder and obtained by curing the described binder composition.

In a preferred embodiment, the density of the mineral wool product is 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.

In a preferred embodiment, the mineral wool product according to the present invention is an insulating product, in particular having a density of 10 to 200 kg/m3.

In an alternative embodiment, the mineral wool product according to the present invention is a façade panel, in particular having a density of 1000-1200 kg/m3.

In a preferred embodiment, the mineral wool product according to the present invention is an insulating product.

In a preferred embodiment, the loss on ignition (LOI) of a mineral wool product according to the present invention is in the range of 0.1 to 25.0%, such as 0.3 to 18.0%, such as 0.5 up to 12.0%, for example from 0.7 to 8.0% by weight.

In one embodiment, the mineral wool product is a mineral wool insulating product, such as a thermal or sound insulating mineral wool product.

In one embodiment, the mineral wool product is a crop growing medium.

Method for manufacturing a product from mineral wool

The present invention also provides a method for making a mineral wool product by binding mineral fibers with a binder composition.

A particular advantage of the mineral wool product according to the invention is that it does not require high curing temperatures. This not only saves energy, reduces VOCs and eliminates the need for high temperature resistant equipment, but also provides high flexibility in the production of mineral wool products using these binders.

In one embodiment, the method includes the following steps:

- preparation of raw material melt,

- fiberization of the melt with the help of a fiberizing plant for the formation of mineral fibers,

- providing mineral fibers in the form of an assembled web,

- mixing the binder with mineral fibers before, during or after receiving the collected web with the formation of a mixture of mineral fibers and binder,

- curing the mixture of mineral fiber and binder.

In one embodiment, the binder is supplied in close proximity to the fiber forming apparatus, such as a cup spinning apparatus or a cascade spinning apparatus, in any case immediately after fiber formation. After that, the fibers coated with a binder are fed onto a conveyor belt in the form of a web.

The web may be subjected to longitudinal compression or lengthwise compression after fiber formation and before significant curing occurs.

Fiber forming device

There are various types of centrifugal spinning machines for forming fiber from mineral melts.

The conventional centrifugal spinning machine is a cascade spinning machine that includes a top (or first) rotor and a next (or second) rotor, and optionally other subsequent rotors (eg third and fourth rotors) in series. Each rotor rotates about different substantially horizontal axes, and the direction of rotation is opposite to that of each adjacent rotor in sequence. These different horizontal axes are arranged in such a way that the melt poured onto the upper rotor rotates in succession on the peripheral surface of each subsequent rotor, and the fibers are dropped from each subsequent rotor and optionally also from the upper rotor.

In one embodiment, the cascade spinning machine or other spinning machine is positioned so that the fibers are formed from the melt and entrained in the air as a cloud of fibers.

Many fiber formers comprise a disk or cup that rotates about a substantially vertical axis. It is traditional to arrange several such spinning devices in a line, i.e. essentially in the first direction, for example as described in GB-A-926749, US-A-3824086 and WO-A-83/03092.

Typically, an air stream is used associated with one or each of the filament forming rotors, and as fibers are formed, the air stream is carried away from the surface of the rotor.

In one embodiment, the binder and/or additives are added to the cloud of fibers by known methods. The amount of binder and/or additive may be the same for each spinning machine or may be different.

In one embodiment, a hydrocarbon oil may be added to the fiber cloud.

The term "gathered web" as used herein includes any mineral fibers that have been gathered together at the surface, i. they are no longer entrained in the air, such as formed mineral fibres, granules, bundles or recycled web scraps. The collected web may be a primary web formed by collecting fibers on a conveyor belt and provided as starting material without cross weaving or other consolidation.

Alternatively, the collected web may be a secondary web formed by overlapping or otherwise consolidating the primary web. Preferably the assembled web is a primary web (primary web).

In one embodiment, the mixing of the binder with the mineral fibers occurs after the web has been assembled in the following steps:

- exposing the collected mineral fiber web to the disentangling process,

- suspension of mineral fibers in the primary air stream,

- mixing the composition of the binder with the mineral fibers before, during or after the disentangling process to form a mixture of mineral fibers and the binder.

A process for the manufacture of a mineral wool product, including a disentangling process step, is described in EP 10190521, which is incorporated by reference.

In one embodiment, the disentanglement process includes feeding the collected mineral fiber web from a channel with a relatively low air flow rate to a channel with a relatively higher air flow rate. In this embodiment, untangling is believed to occur as the fibers that first enter the channel at a relatively higher airflow rate break away from the subsequent web fibers. This type of disentanglement is particularly effective in producing open fiber bundles rather than compacted clumps, which can lead to uneven distribution of materials in the product.

According to a particularly preferred embodiment, the disentangling process comprises feeding the collected web to at least one roller which rotates about its longitudinal axis and has spikes protruding from its peripheral surface. In this embodiment, the rotating roller typically also contributes, at least in part, to a relatively higher airflow rate. Often the rotation of the roller is the only source of the relatively higher airflow rate.

In preferred embodiments, the mineral fibers and optionally the binder are fed to the roll from above. In addition, it is preferable that the untangled mineral fibers and optionally the binder are thrown off the roller in a lateral direction from the lower part of its circumference. In the most preferred embodiment, the mineral fibers rotate approximately 180 degrees on the roll before they are shed.

The binder may be mixed with the mineral fibers before, during or after the disentangling process. In some embodiments, the binder is preferably mixed with the fibers prior to the disentangling process. In particular, the fibers may be in the form of an uncured collected web containing a binder.

It is also possible to premix the binder with the collected mineral fiber web prior to the untangling process. Additional mixing can be carried out during the disentangling process and after it. Alternatively, the binder may be fed into the primary air stream separately and mixed with the primary air stream.

The mixture of mineral fibers and binder is collected from the primary air stream by any suitable method. In one embodiment, the primary air flow is directed to the top of the cyclone chamber, which is open at the bottom end, and the mixture is collected from the bottom end of the cyclone chamber.

The mixture of mineral fibers and binder is preferably withdrawn from the disentanglement process into the forming chamber.

After applying the disentanglement process, the mixture of mineral fibers and binder is collected, pressed and cured. Preferably, the mixture is collected on a perforated conveyor belt under which suction means are located.

In a preferred process according to the invention, the mixture of binder and mineral fibers is compressed and cured after collection.

In a preferred method according to the invention, the mixture of binder and mineral fibers is separated from the substrate after collection and then pressed and cured.

The method can be carried out as a batch process, however, in accordance with one embodiment, the method is carried out in a line for the manufacture of a mineral wool product with the supply of a primary or secondary mineral wool web in a fiber separation process, which provides a particularly economical and versatile method for obtaining composite materials having favorable mechanical properties and thermal insulation properties in a wide range of density values.

At the same time, given that the curing takes place at ambient temperature, the likelihood of spots of uncured binder is significantly reduced.

Curing

The web is cured by chemical and/or physical reaction of the binder components.

In one embodiment, curing occurs in a curing device.

In one embodiment, the curing is carried out at a temperature of from 5 to 150°C, for example, from 5 to 60°C, for example, from 20 to 40°C.

The curing process can begin immediately after the binder has been applied to the fibres.

In one embodiment, the curing process includes crosslinking and/or incorporating water in the form of water of crystallization.

In one embodiment, the cured binder contains water of crystallization, the content of which may decrease or increase depending on the prevailing conditions of temperature, pressure and humidity.

In one embodiment, curing occurs in a conventional mineral wool kiln operating at 5 to 150°C, eg 5 to 60°C, eg 20 to 40°C.

In one embodiment, the curing process includes a drying process.

In a preferred embodiment, the curing of the binder in contact with the mineral fibers takes place in a heat press.

The curing of the binder in contact with the mineral fibers in a heat press has a particular advantage in that it makes it possible to obtain products with a high density.

In one embodiment, the curing process includes pressure drying. Pressure can be applied by blowing air or gas through the mixture of mineral fiber and binder. The purge process may be accompanied by heating or cooling, or may take place at ambient temperature.

In one embodiment, the curing process takes place in a humid environment.

The humid environment may have a relative humidity RH of 60-99%, such as 70-95%, such as 80-92%. Curing in a humid environment may be followed by curing or drying to achieve a state of prevailing moisture.

The mineral wool product may be of any conventional configuration, such as a mat or slab, and may be cut and/or formed (eg, into pipe sections) before, during, or after the binder has cured.

The present invention also provides the use of a binder composition as described above for the manufacture of a mineral fiber article.

In one embodiment, the present invention provides the use of compounds containing one or more M ²⁺ divalent metal cations in a formaldehyde-free mineral fiber binder composition containing at least one phenol-containing compound and at least one protein to improve water absorption. and/or mechanical properties and/or aging properties of a mineral wool product containing mineral fibers bonded together with a binder resulting from the curing of such a binder composition.

In one embodiment, the present invention provides for the use of one or more compounds containing divalent metal cations M ²⁺ and one or more compounds containing monovalent cations M ⁺ , in a formaldehyde-free mineral fiber binder composition containing at least one a phenol-containing compound and at least one protein, for improving water absorption and/or mechanical properties and/or aging properties of a mineral wool product containing mineral fibers bonded together with a binder obtained by curing such a binder composition.

In one embodiment, the compound containing the divalent metal cation M ²⁺ includes Ca ²⁺ .

In one embodiment, the monovalent metal cation-containing compound is in the form of a monovalent metal cation Li, Na, K, in particular Na.

Advantages of the binder composition

The mineral wool product according to the present invention has the unexpected advantage that it can be made with a very simple binder requiring only three components, namely at least one protein, at least one phenol-containing compound and at least one divalent compound containing the metal cation M ²⁺ . Therefore, the mineral wool product according to the present invention is made from natural and non-toxic ingredients and is therefore safe to handle. At the same time, the mineral wool product according to the present invention is made from a binder based on renewable resources, resulting in improved properties of the mineral wool product.

An additional advantage is the ability to cure at or near ambient temperature. This not only results in energy savings and less complexity in the equipment required, but also reduces the chance of uncured binder spots that can occur with thermally cured traditional binders.

An additional benefit is the greatly reduced risk of burnout.

Burn-in (internal combustion) can be associated with exothermic reactions during the manufacture of the mineral wool product, which increase the temperature through the thickness of the insulation, causing the mineral fibers to melt or devitrify and eventually creating a fire hazard. In the worst case, burnout causes stacked pallets to ignite when stored in warehouses or in transit.

Another advantage is the absence or greatly reduced emissions during curing, in particular the absence or greatly reduced emissions of VOCs.

Another important advantage is the self-healing ability of mineral wool products made from binders.

Another advantage of mineral wool products made with the binder according to the present invention is that they show improved properties, in particular with regard to water absorption and/or mechanical properties and/or aging properties, compared to previously known products made of mineral wool, in particular when compared to previously known mineral wool products made from binders derived from renewable resources. This opens up the possibility of custom-made products, such as pipe sections.

Examples

In the following examples, several binders falling within the definition of the present invention were prepared and compared with prior art binders.

Experimental methods and definitions

General experimental methods

IMAGEL® LA gelatin (type A, porcine, 120 Bloom) and IMAGEL® LB gelatin (type B, porcine, 122 Bloom) were obtained from GELITA AG. Sericin (Bombyx mori, silkworm) was obtained from Sigma-Aldrich. Chestnut tree tannin (Vinoferm Tannorouge, food grade) was obtained from Brouwland bvba. Quebracho tannin (Tannivin® Structure, high proanthocyanidin content) was obtained from Erbslöh. 75% aq. glucose syrup with a DE value of 95 to less than 100 (C*sweet D 02767 ex Cargill) was supplied by Cargill. Silane (Momentive VS-142) was supplied by Momentive. 50% aq. hypophosphorous acid, 28% aq. ammonia and all other high purity components were obtained from Sigma-Aldrich. All components, the concentration of which is not indicated above, for simplicity, were considered to be completely pure and anhydrous.

pH measurements were performed using a Mettler Toledo SevenCompactTM S220 pH meter equipped with a Mettler Toledo InLab® Expert Pro-ISM pH electrode and temperature sensor.

The stone pellets (predominantly rounded particles having the same melt composition as stone wool fibers) resulting from the stone melt cascade formation process in the manufacture of stone wool fibers were obtained from the ROCKWOOL® plant in the Netherlands. The crude mixture of stone granules was first sieved to remove granules >1.2 mm in diameter as well as any remaining stone wool tufts. The stone pellets were then heat treated overnight at 590° C. to remove any traces of organic matter. After cooling, the stone granules were screened again, this time separating fractions with a diameter of 0.25-0.50 mm, and fractions of a smaller or larger diameter were discarded. Fractions of stone granules with a diameter of 0.25-0.50 mm were thoroughly washed first in cold tap water and then in demineralized water. The screened and cleaned stone pellets were dried overnight at 120° C., allowed to cool to ambient temperature, and then stored at ambient temperature in a closed container until use.

FUNKTION heat-resistant silicone molds for making bars (4×5 slits in the mold; top slit size: length = 5.6 cm, width = 2.5 cm; bottom slit size: length = 5.3 cm, width = 2.2 cm ; slot height = 1.1 cm) was obtained from F&H of Scandinavia A/S.

Three-point bending tests were recorded on a Bent Tram SUT 3000/520 testing machine (test speed: 10.0 mm/min, breaking level: 50 N, nominal force: 30 N/mm2, distance between supports: 40 mm, maximum deflection 20 mm, nominal modulus of elasticity 10000 N/mm2). The bars were placed in the machine with the "top side" facing up (i.e. face with length = 5.6 cm and width = 2.5 cm).

New tin foil containers for use in measuring binder solids (reference binders A and B only) and loss on ignition of composite bars were heat treated at 590°C for 15 minutes prior to use to remove all organics.

Binder Solids Content - Definition

The content of each of the components in a given binder solution prior to curing is based on the anhydrous weight of the components. You can use the following formula:

Binder Solids Content (%) = [(Binder Component A Solids (g) + Binder Component B Solids (g)+…)/Total Blend Weight (g)] × 100%.

Binder Solids - Definition and Procedure (reference binders A and B only)

The content of the binder after curing is referred to as "binder solids".

Disc-shaped stone wool samples (diameter: 5 cm, height 1 cm) were cut from the stone wool and heat treated at 590° C. for at least 30 minutes to remove all organic matter. Binder mixture solids (see below for examples of mixtures) was measured by spreading a sample of the binder mixture (about 2 g) over a heat-treated stone wool disc in a foil container. The weight of the foil container containing the stone wool disc was determined before and immediately after the addition of the binder mixture. Two such stone wool disks were made with a binder mixture applied in foil containers and heated at 200° C. for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the binder solid was calculated as the average of the two results.

Reaction Loss - Definition (reference binders A and B only)

Reaction loss is defined as the difference between the solids content of the binder components and the solids content of the binder.

Production of composite bars

15 wt. % binder solution or 15% binder solids solution (reference binders A and B only) were prepared as described in the examples below. A sample of the binder solution (16.0 g) was mixed well with the granules (90.0 g). Then, the resulting mixture was poured into four compartments in a heat-resistant silicone mold for the manufacture of bars. In the manufacture of each composite bar, the mixtures placed in the compartments were pressed, if necessary, and then leveled with a plastic spatula to obtain a smooth surface of the bar. In total, 28-32 bars were made in this way from each binder composition. The production of surplus bars made it possible to eliminate bars that had visual irregularities, such as surface irregularities, cracks and/or air pockets formed during the manufacturing process. Bars made using reference binder A were cured for 1 hour at 200°C, and bars made using reference binder B were cured for 1 hour at 225°C. Binders in accordance with the present invention, as well as all other reference binders were cured and dried at room temperature for 2-3 days. The bars were carefully removed from the containers, turned upside down and left for another 1-2 days at room temperature for complete curing and drying.

Aging of composite bars

Aging of the composite bars was carried out by autoclaving the bars (15 min / 120°C / 1.2 bar) or water bath treatment (3 hours / 80°C) followed by cooling to room temperature and drying for 2-3 days.

Measuring the mechanical strength of composite bars

The maximum load force required to break composite bars was recorded in a three-point bend test. For each data point, the mean value was calculated based on five columns subjected to identical processing.

Measurement of loss on ignition (LOI) of composite bars

Loss on ignition (LOI) composite bars were measured in small tin foil containers when heated to 590°C. A tin foil container was weighed and four bars were placed in it (usually after breaking in a 3-point bend test). Then, the container with bars was weighed and subjected to heat treatment at 590°C for 30 minutes. After cooling to room temperature, the mass was recorded again and the loss on ignition (LOI) was calculated using the following formula:

Water absorption measurements

The water absorption of the binders was measured by weighing three bars and then immersing them in water (about 250 ml) in a beaker (565 ml, bottom Ø=9.5 cm, top Ø=10.5 cm, height=7.5 cm) for 3 hours or 24 hours. The bars were placed next to each other on the bottom of the glass "upper surface" down (ie surface with dimensions length=5.6 cm, width=2.5 cm). After the set time, the bars were lifted one by one and left for one minute to drain the water. The bars were held (carefully) with the long side almost vertical so that drops dripped from the corner of the bar. Then the bars were weighed and the water absorption was calculated using the following formula:

Prior Art Reference Binder Compositions and Reference Binders

Reference binder, example A (urea-modified phenol-formaldehyde resin, PUF-resol)

Phenol-formaldehyde resin was obtained by the reaction of 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 heating at a rate of about 1°C per minute. The reaction was continued at 84°C until the acid resistance of the resin reached 4 and most of the phenol was consumed. Urea (241 g) was then added and the mixture was cooled.

Acid resistance (AT) shows how many times a given volume of a binder can be diluted with acid without clouding the mixture (precipitation of the binder). Sulfuric acid was used to determine the stop criterion in the production of the binder, and acid resistance below 4 indicates completion of the binder reaction. To measure AT, a titration solution was prepared by diluting 2.5 ml of conc. sulfuric acid (>99%) 1 l water, purified by ion exchange. 5 ml of the test binder was further titrated at room temperature with this titration solution, keeping the binder in motion by manual shaking; if desired, a magnetic stirrer and a magnetic stir bar can be used. The titration is continued until a slight turbidity appears, which does not disappear when the binder is shaken.

Acid resistance (AT) is calculated by dividing the amount of acid used for titration (ml) by the amount of sample (ml):

AT = (volume of titration solution used (ml)) / (sample volume (ml))

Using the resulting urea-modified phenol-formaldehyde resin, a binder was prepared by adding 25% aq. a solution of ammonia (90 ml) and ammonium sulfate (13.2 g), followed by the addition of water (1.30 kg). Then, binder solids were measured as described above and the mixture was diluted with the required amount of water and silane (Momentive VS-142) to study mechanical strength (15% binder solids solution, 0.5% silane from binder solids) .

Reference binder example B

A mixture of 75% aq. glucose syrup (38.9 g), ammonium sulfamate (1.17 g), 50% hypophosphorous acid (0.58 g) and urea (1.46 g) in water (106.4 g) were stirred at room temperature until clear solution. Then 28% aq. ammonia (0.38 g) followed by the addition of 10% Momentive VS-142 silane (1.13 g). The final binder mixture contained 15% binder solids and had a pH of 8.

Reference binder example F

To a 1M NaOH solution (31.5 g) stirred at room temperature was added chestnut tree tannin (9.00 g). After stirring at room temperature for another 5-10 min, the resulting dark brown solution was used in subsequent experiments.

A mixture of IMAGEL® LA gelatin (12.00 g) and water (68.54 g) was stirred at 50° C. for approx. 15-30 min until a clear solution is obtained (pH 4.7). 1M NaOH (3.90 g) (pH 9.0) was then added, followed by a portion of the above chestnut tree tannin solution (5.40 g; thus, effectively 1.20 g of chestnut tree tannin). After stirring for another 1-2 minutes at 50° C., the resulting brown mixture (pH 9.2) was used in subsequent experiments.

Binder compositions according to the present invention

Binder Example Example 8

To a stirred solution of NaOH (4.00 g, 0.10 mol) in water (200 ml) at room temperature was added Ca(OH) ₂ (3.70 g, 0.05 mmol). After stirring at room temperature for another 5-10 min, the resulting colorless suspension was used in subsequent experiments (with constant stirring).

To a portion of the above mixture of Ca(OH) ₂ -NaOH (31.5 g) stirred at room temperature was added chestnut tree tannin (9.00 g). After stirring at room temperature for 5-10 minutes, the resulting dark brown mixture (pH 8.8) was used in subsequent experiments.

A mixture of IMAGEL® LA gelatin (12.00 g) and water (66.43 g) was stirred at 50° C. for approx. 15-30 min until a clear solution is obtained (pH 4.9). A portion of the above mixture of Ca(OH) ₂ -NaOH (4.78 g) (pH 9.4) was then added, followed by a portion of the above mixture of chestnut tannins (2.70 g; thus effectively 0.60 g of chestnut tannin tree). After stirring for another 1-2 minutes at 50° C., the resulting brown mixture (pH 9.1) was used in subsequent experiments.

Binder Example Example 14

To a stirred solution of NaOH (2.00 g, 0.05 mol) in water (200 ml) at room temperature was added Ca(OH) ₂ (5.56 g, 0.075 mmol). After stirring at room temperature for another 5-10 min, the resulting colorless suspension was used in subsequent experiments (with constant stirring).

To a portion of the above mixture of Ca(OH) ₂ -NaOH (31.5 g) stirred at room temperature was added chestnut tree tannin (9.00 g). After stirring at room temperature for another 5-10 minutes, the resulting dark brown mixture (pH 8.4) was used in further experiments.

A mixture of IMAGEL® LA gelatin (12.00 g) and water (68.00 g) was stirred at 50° C. for approx. 15-30 min until a clear solution is obtained (pH 5.2). A portion of the above mixture of Ca(OH) ₂ -NaOH (5.19 g) (pH 9.6) was then added, followed by a portion of the above mixture of chestnut tannins (5.40 g; thus effectively 1.20 g of chestnut tannin tree). After stirring for another 1-2 minutes at 50° C., the resulting brown mixture (pH 9.0) was used in subsequent experiments.

Binder Example Example 17

To water (200 ml) stirred at room temperature was added Ca(OH) ₂ (7.41 g, 0.10 mmol). After stirring at room temperature for another 5-10 min, the resulting colorless suspension was used in subsequent experiments (with constant stirring).

To a portion of the above Ca(OH) ₂ mixture (31.5 g) stirred at room temperature was added chestnut tree tannin (9.00 g). After stirring at room temperature for 5-10 minutes, the resulting dark brown mixture (pH 8.0) was used in subsequent experiments.

A mixture of IMAGEL® LA gelatin (12.00 g) and water (65.42 g) was stirred at 50° C. for approx. 15-30 min until a clear solution is obtained (pH 5.0). A portion of the above mixture of Ca(OH) ₂ (5.13 g) (pH 9.5) was then added, followed by a portion of the above mixture of chestnut tannins (1.62 g; thus effectively 0.36 g of chestnut tannin) . After stirring for another 1-2 minutes at 50° C., the resulting brown mixture (pH 9.2) was used in subsequent experiments.

Binder Example Example 20

To water (200 ml) stirred at room temperature was added Ca(OH) ₂ (7.41 g, 0.10 mmol). After stirring at room temperature for another 5-10 min, the resulting colorless suspension was used in subsequent experiments (with constant stirring).

To a portion of the above Ca(OH) ₂ mixture (31.5 g) stirred at room temperature was added chestnut tree tannin (9.00 g). After stirring at room temperature for 5-10 minutes, the resulting dark brown mixture (pH 8.0) was used in subsequent experiments.

A mixture of IMAGEL® LA gelatin (11.00 g) and water (62.83 g) was stirred at 50° C. for approximately 15-30 minutes until a clear solution (pH 5.1) was obtained. A portion of the above mixture of Ca(OH) ₂ (8.21 g) (pH 11.1) was then added, followed by a portion of the above mixture of chestnut tree tannins (9.90 g; thus effectively 2.20 g of chestnut tree tannin) . After stirring for another 1-2 minutes at 50° C., the resulting brown mixture (pH 9.0) was used in subsequent experiments.

Binder Example Example 22

To a stirred solution of NaOH (2.00 g, 0.05 mol) in water (200 ml) at room temperature was added Ca(OH) ₂ (5.56 g, 0.075 mmol). After stirring at room temperature for another 5-10 min, the resulting colorless suspension was used in subsequent experiments (with constant stirring).

To a portion of the above mixture of Ca(OH) ₂ -NaOH (31.5 g) stirred at room temperature was added chestnut tree tannin (9.00 g). After stirring at room temperature for another 5-10 minutes, the resulting dark brown mixture (pH 8.4) was used in further experiments.

A mixture of IMAGEL® LA gelatin (7.50 g) and sericin (2.50 g) in water (56.23 g) was stirred at 50° C. for approximately 15-30 minutes until a clear solution (pH 5.6) was obtained. A portion of the above mixture of Ca(OH) ₂ -NaOH (4.55 g) (pH 9.3) was then added, followed by a portion of the above mixture of chestnut tannins (5.40 g; thus effectively 1.20 g of chestnut tannin tree). After stirring for another 1-2 minutes at 50° C., the resulting brown mixture (pH 9.1) was used in subsequent experiments.

Binder Example Example 23

To a stirred solution of NaOH (2.00 g, 0.05 mol) in water (200 ml) at room temperature was added Ba(OH) ₂ (12.85 g, 0.075 mmol). After stirring at room temperature for another 5-10 min, the resulting colorless suspension was used in subsequent experiments (with constant stirring).

To a portion of the above mixture of Ba(OH) ₂ -NaOH (31.5 g) stirred at room temperature was added chestnut tree tannin (9.00 g). After stirring at room temperature for an additional 5-10 minutes, the resulting brown mixture (pH 8.6) was used in subsequent experiments.

A mixture of IMAGEL® LA gelatin (12.00 g) and water (70.19 g) was stirred at 50° C. for about 15-30 minutes until a clear solution (pH 4.9) was obtained. Next, a portion of the above mixture of Ba(OH) ₂ -NaOH (4.77 g) (pH 9.2) was added, followed by a portion of the above mixture of chestnut tannins (5.40 g; thus, effectively 1.20 g of tannin chestnut tree). After stirring for another 1-2 minutes at 50° C., the resulting brown mixture (pH 9.0) was used in subsequent experiments.

Binder Example Example 25

To a stirred solution of NaOH (1.00 g, 0.025 mol) in water (200 ml) at room temperature was added Ca(OH) ₂ (2.79 g, 0.038 mmol). After stirring at room temperature for another 5-10 min, the resulting colorless suspension was used in subsequent experiments (with constant stirring).

To a portion of the above Ca(OH) ₂ -NaOH mixture (31.5 g) stirred at room temperature was added quebracho tannin (9.00 g). After stirring at room temperature for 5-10 minutes, the resulting brown mixture (pH 8.8) was used in subsequent experiments.

A mixture of IMAGEL® LA gelatin (12.00 g) and water (63.47 g) was stirred at 50° C. for approximately 15-30 minutes until a clear solution (pH 4.9) was obtained. A portion of the above mixture of Ca(OH) ₂ -NaOH (8.68 g) (pH 9.2) was then added, followed by a portion of the above mixture of chestnut tannins (5.40 g; thus effectively 1.20 g of quebracho tannin ). After stirring for another 1-2 minutes at 50° C., the resulting brown mixture (pH 9.0) was used in subsequent experiments.

Table 1-1. Binder compositions according to the prior art Example A B Binding Properties Binder solids (%) 15.0 15.0 Loss in reaction (%) 28.5 30.3 pH 9.6 8 Bar curing conditions Temperature (°C / 1 h) 200 225 Bar properties Mechanical strength, not aged (kN) 0.52 0.37 Mechanical strength, aging in a water bath (kN) 0.35 0.29 LOI, not aged (%) 2.6 2.4 LOI water aged (%) 2.6 2.4 Water absorption, 3 h (%) 21 23 Water absorption, 24 h (%) 21 24

Table 1-2. Reference binders (protein, crosslinker, sodium hydroxide) Example C D E F G Binder compositions Protein (wt%) ^[a] Gelatin IMAGEL® LA 100 100 100 100 100 Gelatin IMAGEL® LB - - - - - Sericin - - - - - Crosslinker (wt %) ^[a] chestnut tree tannin - 3 5 10 20 tannin quebracho - - - - - Monovalent metal cation compound (wt %) ^[b] Sodium hydroxide 1.2 1.6 1.8 2.4 3.3 Divalent metal cation compound (wt %) ^[b] calcium hydroxide - - - - - barium hydroxide - - - - - magnesium hydroxide - - - - - Monovalent and divalent metal cations (molar ratios) Sodium 100 100 100 100 100 Calcium 0 0 0 0 0 Barium 0 0 0 0 0 Magnesium 0 0 0 0 0 Binder mixing and bar production The content of the solid components of the binder (%) 15.0 15.0 15.0 15.0 15.0 binder pH 9.1 9.0 9.0 9.2 9.2 Curing temperature (°C) room room room room room Bar properties Mechanical strength, not aged (kN) 0.32 0.34 0.32 0.31 0.25 Mechanical strength, aging in a water bath (kN) 0 0.28 0.29 0.27 0.26 Mechanical strength, autoclave (kN) 0.25 0.24 0.23 0.19 0.19 LOI, not aged (%) 2.5 2.5 2.5 2.5 2.5 LOI, water bath (%) 0 2.2 2.3 2.3 2.3 LOI, autoclave aging (%) 2.5 2.5 2.5 2.5 2.4 Water absorption, 3 h (%) 5 8 7 8 eleven Water absorption, 24 h (%) 12 18 17 19 25

[a] Protein. [b] Protein + crosslinker.

Table 1-3. Reference binders (protein, crosslinker, sodium hydroxide) Example H I J K L Binder compositions Protein (wt%) ^[a] Gelatin IMAGEL® LA 100 100 - 75 100 Gelatin IMAGEL® LB - - 100 - - Sericin - - - 25 - Cross-linking agent (% wt.) ^[a] chestnut tree tannin thirty 50 10 12 - tannin quebracho - - - - 10 Monovalent metal cation compound (wt %) ^[b] Sodium hydroxide 4.1 5.3 2.5 2.4 1.7 Divalent metal cation compound (wt %) ^[b] calcium hydroxide - - - - - barium hydroxide - - - - - magnesium hydroxide - - - - - Monovalent and divalent metal cations (molar ratios) Sodium 100 100 100 100 100 Calcium 0 0 0 0 0 Barium 0 0 0 0 0 Magnesium 0 0 0 0 0 Binder mixing and bar production Binder solids content (%) 15.0 15.0 15.0 15.0 15.0 binder pH 9.2 9.1 9.2 9.1 9.0 Curing temperature (°C) room room room room room Bar properties Mechanical strength, not aged (kN) 0.16 0.10 0.34 0.26 0.33 Mechanical strength, aging in a water bath (kN) 0.17 0.10 0.22 0.22 0.26 Mechanical strength, autoclave (kN) 0.12 0.08 0.23 - 0.25 LOI, not aged (%) 2.4 2.4 2.5 2.6 2.5 LOI, water bath (%) 2.2 2.1 2.4 2.3 2.4 LOI, autoclave aging (%) 2.4 2.3 2.5 - 2.5 Water absorption, 3 h (%) 13 15 16 14 6 Water absorption, 24 h (%) 29 33 38 34 16

[a] Protein. [b] Protein + crosslinker.

Table 1-4. Protein, crosslinker, calcium hydroxide-sodium hydroxide Example 1 2 3 4 5 binder compositions Protein (wt%) ^[a] Gelatin IMAGEL® LA 100 100 100 100 100 Gelatin IMAGEL® LB - - - - - Sericin - - - - - Cross-linking agent (% wt.) ^[a] chestnut tree tannin - 3 5 10 20 tannin quebracho - - - - - Monovalent metal cation compound (wt %) ^[b] Sodium hydroxide 1.2 1.7 2.0 2.5 3.3 Divalent metal cation compound (wt %) ^[b] calcium hydroxide 0.4 0.5 0.6 0.8 1.0 barium hydroxide - - - - - magnesium hydroxide - - - - - Monovalent and divalent metal cations (molar ratios) Sodium 85.7 85.7 85.7 85.7 85.7 Calcium 14.3 14.3 14.3 14.3 14.3 Barium - - - - - Magnesium - - - - - Binder mixing and bar production Binder solids content (%) 15.0 15.0 15.0 15.0 15.0 binder pH 9.0 9.0 9.1 9.1 9.0 Curing temperature (°C) room room room room room Bar properties Mechanical strength, not aged (kN) 0.29 0.32 0.32 0.29 0.20 Mechanical strength, aging in a water bath (kN) 0 0.23 0.29 0.31 0.24 Mechanical strength, autoclave (kN) 0.25 0.20 0.18 0.18 0.12 LOI, not aged (%) 2.5 2.5 2.5 2.5 2.4 LOI, water bath (%) 0 2.0 2.2 2.3 2.3 LOI, autoclave aging (%) 2.5 2.5 2.5 2.4 2.4 Water absorption, 3 h (%) 5 7 7 8 10 Water absorption, 24 h (%) 12 18 18 20 24

[a] Protein. [b] Protein + crosslinker.

Table 1-5. Protein, crosslinker, calcium hydroxide-sodium hydroxide Example 6 7 8 9 10 Binder compositions Protein (wt%) ^[a] Gelatin IMAGEL® LA 100 100 100 100 100 Gelatin IMAGEL® LB - - - - - Sericin - - - - - Cross-linking agent (% wt.) ^[a] chestnut tree tannin - 3 5 10 20 tannin quebracho - - - - - Monovalent metal cation compound (wt %) ^[b] Sodium hydroxide 0.6 0.9 1.1 1.3 1.8 Divalent metal cation compound (wt %) ^[b] calcium hydroxide 0.5 0.8 1.0 1.2 1.7 barium hydroxide - - - - - magnesium hydroxide - - - - - Monovalent and divalent metal cations (molar ratios) Sodium 66.7 66.7 66.7 66.7 66.7 Calcium 33.3 33.3 33.3 33.3 33.3 Barium - - - - - Magnesium - - - - - Binder mixing and bar production Binder solids content (%) 15.0 15.0 15.0 15.0 15.0 binder pH 9.0 9.0 9.1 9.1 9.0 Curing temperature (°C) room room room room room Bar properties Mechanical strength, not aged (kN) 0.31 0.35 0.36 0.32 0.32 Mechanical strength, aging in a water bath (kN) 0 0.03 0.21 0.26 0.29 Mechanical strength, autoclave (kN) 0.33 0.30 0.27 0.25 0.23 LOI, not aged (%) 2.6 2.6 2.5 2.5 2.5 LOI, water bath (%) 0 0.8 2.0 2.2 2.3 LOI, autoclave aging (%) 2.5 2.5 2.5 2.5 2.5 Water absorption, 3 h (%) 5 5 5 6 7 Water absorption, 24 h (%) 10 eleven 13 15 17

[a] Protein. [b] Protein + crosslinker.

Table 1-6. Protein, crosslinker, calcium hydroxide-sodium hydroxide Example eleven 12 13 14 15 Binder Composition Protein (wt%) ^[a] Gelatin IMAGEL® LA 100 100 100 100 100 Gelatin IMAGEL® LB - - - - - Sericin - - - - - Cross-linking agent (% wt.) ^[a] chestnut tree tannin - 3 5 10 20 tannin quebracho - - - - - Monovalent metal cation compound (wt %) ^[b] Sodium hydroxide 0.3 0.4 0.5 0.7 1.0 Divalent metal cation compound (wt %) ^[b] calcium hydroxide 0.9 1.2 1.4 1.9 2.8 barium hydroxide - - - - - magnesium hydroxide - - - - - Monovalent and divalent metal cations (molar ratios) Sodium 40 40 40 40 40 Calcium 60 60 60 60 60 Barium - - - - - Magnesium - - - - - Binder mixing and bar production Binder solids content (%) 15.0 15.0 15.0 14.9 15.0 binder pH 9.1 9.1 9.0 9.0 9.1 Curing temperature (°C) room room room room room Bar properties Mechanical strength, not aged (kN) 0.31 0.34 0.34 0.32 0.27 Mechanical strength, aging in a water bath (kN) 0 0 0.16 0.26 0.29 Mechanical strength, autoclave (kN) 0.27 0.28 0.29 0.23 0.18 LOI, not aged (%) 2.5 2.5 2.5 2.5 2.4 LOI, water bath (%) 0 0 1.6 2.1 2.2 LOI, autoclave aging (%) 2.5 2.4 2.4 2.4 2.4 Water absorption, 3 h (%) 4 4 4 4 5 Water absorption, 24 h (%) 9 9 10 10 eleven

[a] Protein. [b] Protein + crosslinker.

Table 1-7. Protein, crosslinker, calcium hydroxide Example 16 17 18 19 20 Binder Composition Protein (wt%) ^[a] Gelatin IMAGEL® LA 100 100 100 100 100 Gelatin IMAGEL® LB - - - - - Sericin - - - - - Cross-linking agent (% wt.) ^[a] chestnut tree tannin - 3 5 10 20 tannin quebracho - - - - - Monovalent metal cation compound (wt %) ^[b] Sodium hydroxide 0 0 0 0 0 Divalent metal cation compound (wt %) ^[b] calcium hydroxide 1.2 1.8 2.0 2.8 4.3 barium hydroxide - - - - - magnesium hydroxide - - - - - Monovalent and divalent metal cations (molar ratios) Sodium 0 0 0 0 0 Calcium 100 100 100 100 100 Barium - - - - - Magnesium - - - - - Binder mixing and bar production Binder solids content (%) 15.0 15.0 15.0 15.0 15.0 binder pH 9.0 9.2 9.0 9.0 9.0 Curing temperature (°C) room room room room room Bar properties Mechanical strength, unaged (kN) 0.34 0.37 0.37 0.36 0.33 Mechanical strength, aging in a water bath (kN) 0 0 0 0.27 0.29 Mechanical strength, autoclave (kN) 0.36 0.34 0.26 0.23 0.16 LOI, not aged (%) 2.7 2.6 2.5 2.5 2.5 LOI, water bath (%) 0 0 0 2.0 2.2 LOI, autoclave aging (%) 2.6 2.5 2.5 2.5 2.4 Water absorption, 3 h (%) 4 4 4 4 4 Water absorption, 24 h (%) 9 8 8 9 9

[a] Protein. [b] Protein + crosslinker.

Table 1-8. Protein, cross-linking agent, hydroxide M ²⁺ -sodium hydroxide Example 21 22 23 24 25 Binder Composition Protein (wt%) ^[a] Gelatin IMAGEL® LA - 75 100 100 100 Gelatin IMAGEL® LB 100 - - - - Sericin - 25 - - - Cross-linking agent (% wt.) ^[a] chestnut tree tannin 10 12 10 10 - tannin quebracho - - - - 10 Monovalent metal cation compound (wt %) ^[b] Sodium hydroxide 0.7 0.8 0.6 2.0 0.5 Divalent metal cation compound (wt %) ^[b] calcium hydroxide 2.1 2.1 - - 1.3 barium hydroxide - - 4.1 - - magnesium hydroxide - - - 4.3 - Monovalent and divalent metal cations (molar ratios) Sodium 40 40 40 40 40 Calcium 60 60 0 0 60 Barium 0 0 60 0 0 Magnesium 0 0 0 60 0 Binder mixing and bar production Binder solids content (%) 15.0 15.1 15.0 14.7 15.0 binder pH 9.0 9.1 9.0 9.0 9.0 Curing temperature (°C) room room room room room Bar properties Mechanical strength, not aged (kN) 0.39 0.27 0.35 0.31 0.31 Mechanical strength, aging in a water bath (kN) 0.15 0.18 0.26 0.28 0.25 Mechanical strength, autoclave (kN) 0.28 - 0.25 0.20 0.25 LOI, not aged (%) 2.6 2.6 2.5 2.4 2.5 LOI, water bath (%) 2.1 2.0 2.3 2.3 2.4 LOI, autoclave aging (%) 2.5 - 2.4 2.4 2.5 Water absorption, 3 h (%) 10 8 7 7 4 Water absorption, 24 h (%) 25 20 15 17 10

[a] Protein. [b] Protein + crosslinker.

Claims (24)

1. A formaldehyde-free mineral fiber binder composition comprising: - at least one phenol-containing compound, - at least one protein, - at least one compound containing the divalent metal cation M ²⁺ , - at least one compound containing the monovalent metal cation M ⁺ . 2. The binder composition according to claim 1, in which at least one compound containing the divalent metal cation M ²⁺ contains one or more divalent metal cations M ²⁺ selected from the group of divalent alkaline earth metal cations, Mn, Fe , Cu, Zn, Sn. 3. The binder composition according to any of the preceding claims, wherein the compound containing the divalent metal cation M ²⁺ contains one or more compounds selected from the group consisting of M(OH) ₂ , MO, M(HCO ₃ ) ₂ , MCO ₃ , M(H ₂ PO ₄ ) ₂ , MHPO ₄ , M ₃ (PO ₄ ) ₂ , M(HPO ₃ ), M(H ₂ PO ₂ ) ₂ , MSO ₄ , MCl ₂ , MHNSO ₃ , in particular M (OH) ₂ . 4. A binder composition according to any one of the preceding claims, wherein the divalent metal cation containing compound contains Ca ²⁺ . 5. The binder composition according to any of the preceding claims, characterized in that the binder composition contains at least one compound with a divalent metal cation in an amount of from 0.1 wt.% to 10 wt.%, for example from 0.2 wt. % to 8 wt.%, for example from 0.3 wt.% to 5 wt.%, for example from 0.4 wt.% to 4.3 wt.%, for example from 1.0 wt.% to 4.3 wt. .%, based on the total dry weight of the phenol-containing compound and protein. 6. A binder composition according to any one of the preceding claims, characterized in that the binder composition contains at least one monovalent metal cation in the form of a monovalent metal cation Li, Na, K, in particular Na. 7. A binder composition according to any of the preceding claims, characterized in that the binder composition contains at least one compound containing a monovalent metal cation M ⁺ in an amount of from 0.01 wt.% to 6 wt.%, for example from 0 ,1 wt.% to 5 wt.%, for example 0.2 wt. % to 4 wt.%, for example from 0.3 wt.% to 3.3 wt.%, for example from 0.3 wt.% to 2.0 wt.%, based on the total dry weight of the phenol-containing compound and protein. 8. The binder composition according to any one of the preceding claims, characterized in that the binder composition contains at least one compound containing the divalent metal cation M ²⁺ and at least one compound containing the monovalent metal cation M ⁺ , and where the molar the ratio of divalent metal cation to monovalent metal cation is in the range from 10:90 to 90:10, for example from 14.3:85.7 to 90:10, for example from 14.3:85.7 to 60:40, for example from 20:80 to 80:20, such as 25:75 to 75:25, such as 33.3:66.7 to 60:40, such as 40:60 to 60:40, such as 50:50. 9. The mineral fiber binder composition according to any of the preceding claims, characterized in that at least one phenol-containing compound comprises a phenol-containing compound, such as simple phenols, such as hydroxybenzoic acids, such as hydroxybenzoic aldehydes, such as hydroxyacetophenones, such as hydroxyphenylacetic acids such as cinnamic acids such as cinnamic acid esters such as cinnamic aldehydes such as cinnamic alcohols such as coumarins such as isocoumarins such as chromones such as flavonoids such as chalcones such as dihydrochalcones such as aurones such as flavanones such as flavannols such as flavans such as leucoanthocyanidins such as flavan-3-ols such as flavones such as anthocyanidins such as deoxyanthocyanidins such as anthocyanins such as biflavonyls such as benzophenones, such as xanthones such as stilbenes such as betacyanins such as polyphenols and/or polyhydroxyphenols such as lignans, neolignans (dimers or oligomers resulting from the combination of monolignols such as p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol), such as lignins (synthesized mainly from monolignol precursors p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol), such as tannins, such as tannates (salts of tannins), such as condensed tannins (proanthocyanidins), such as hydrolysable tannins, such as gallotannins, such like ellagitannins such as complex tannins such as tannic acid such as flobabens such as phlorotannins. 10. A mineral fiber binder composition according to claim 9, wherein the tannin is selected from one or more components from the group consisting of tannic acid, condensed tannins (proanthocyanidins), hydrolysable tannins, gallotannins, ellagitannins, complex tannins and/or tannin, derived from one or more of oak, chestnut, staghorn sumac, grandiflora tellima, quebracho, acacia, mimosa, black locust bark, vine, gall, ginger, myrobalan, taro, wallonia and eucalyptus. 11. A mineral fiber binder composition according to any one of the preceding claims, characterized in that the phenol-containing compound comprises one or more synthetic or semi-synthetic molecules containing phenols, polyphenols such as proteins, peptides, peptoids or arylopeptides modified with phenol-containing side chains, such as as dendrimers decorated with phenol-containing side chains. 12. A mineral fiber binder composition according to any one of the above, characterized in that at least one protein is selected from the group consisting of proteins of animal origin, including collagen, gelatin, hydrolysed gelatin and milk protein (casein, whey), eggs ; jellyfish proteins, proteins obtained by recombinant methods; insect proteins such as silkworms such as sericin; proteins from plant sources, including proteins from algae, legumes, cereals, whole grains, nuts, seeds and fruits, such as protein 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, lupins, kidney beans, almonds, Brazil nuts, cashews, pecans, walnuts, canola seeds, cotton seeds, pumpkin seeds, hemp seeds, sesame seeds and sunflower seeds; polyphenolic proteins such as mussel foot protein. 13. A mineral fiber binder composition according to any one of the preceding claims, wherein the content of at least one phenol-containing compound, such as tannin, is from 1 to 60% by weight, for example from 2 to 60% by weight, for example from 3 to 50 wt.%, for example from 4 to 40 wt.%, for example from 5 to 35 wt.%, calculated on a dry protein basis. 14. A mineral fiber binder composition according to any one of the preceding claims, characterized in that the protein contains 50 to 400, for example 100 to 300 (hydroxyproline + proline) residues per 1000 amino acid residues. 15. A binder composition for mineral fibers according to any one of the preceding claims, characterized in that the binder composition further comprises an additive selected from the group of an oxidizing agent such as tyrosinase, a pH adjuster, preferably in the form of a base such as an organic base such as an amine. or its salts, an inorganic base such as ammonia or its salts. 16. A mineral fiber binder composition according to any one of the above, characterized in that the binder composition has a pH greater than 7, such as greater than 8, such as greater than 9, such as in the range of above 7 to below 11. 17. A mineral wool product containing mineral fibers bonded together with a binder, and obtained by curing the binder composition according to any one of paragraphs. 1-16. 18. A method of manufacturing a mineral wool product, which includes the steps of contacting mineral fibers with a binder composition according to any one of claims 1 to 16 and curing the binder. 19. Use of a binder composition according to any one of claims 1 to 16 for the manufacture of a mineral wool product. 20. Use of one or more compounds containing M ⁺ monovalent metal cations and one or more compounds containing M ²⁺ divalent metal cations in a formaldehyde-free mineral fiber binder composition containing at least one phenol-containing compound and at least one protein to improve water absorption and/or mechanical properties and/or aging properties of a mineral wool product containing mineral fibers bonded together with a binder and cured by this binder composition.

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