Aqueous binder composition

Abstract

The present invention relates to a phenol and formaldehyde free aqueous binder composition.

Description

TECHNICAL FIELD

[0001] The present invention relates to an aqueous binder composition for mineral fibres, a process for producing a bonded mineral fibre product using said binder, a mineral fibre product comprising mineral fibres in contact with a cured binder, and the use of a lignin component for the preparation of a binder composition. BACKGROUND

[0003] Mineral fibre products typically comprise man-made vitreous fibres (MMVF) such as glass fibres, ceramic fibres, basalt fibres, slag wool, mineral wool and asbestos which are bonded together by a cured thermoset polymeric binder material. In order to be used as thermal or acoustic insulation products, bonded mineral fibre mats are typically produced by converting a melt made from suitable raw materials into fibres in a conventional manner, for example by a spin cup process or by a cascade rotor process. The fibres are blown into a forming chamber and, while still hot and aerodynamic, sprayed with a binder solution and deposited randomly in the form of a mat or web on a moving conveyor belt. The fibre 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 fibres together.

[0004] In the past, the binder resin of choice was a phenol formaldehyde resin which could be produced economically and which could be augmented with urea prior to use as a binder. However, existing and proposed legislation aimed at reducing or eliminating formaldehyde emissions has led to the development of formaldehyde-free binder compositions such as those based on polycarboxylic polymers and polyols or polyamines (for example the binder compositions disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, US-A-5,318,990 and US-A-2007 / 0173588).

[0005] Another group of non-phenol formaldehyde binders are the addition / elimination reaction products of aliphatic and / or aromatic acid anhydrides with alkanolamines, for example as disclosed in WO99 / 36368, WO01 / 05725, WO01 / 96460, WO02 / 06178, WO2004 / 007615 and WO2006 / 061249. These binder compositions are water soluble and exhibit excellent bonding properties in terms of speed of cure and density of cure. WO2008 / 023032 discloses a urea modified binder of that type which provides a mineral wool product having reduced moisture absorption.

[0006] There is an ongoing need to provide formaldehyde-free binders which can be produced economically since some of the starting materials used to produce these binders are quite expensive chemicals.

[0007] Another effect associated with the previously known aqueous binder compositions for mineral fibres is that at least a large part of the starting materials used for the production of these binders originates from fossil fuels. There has been a tendency for a long time for consumers to prefer products produced entirely or at least partially from renewable materials, and thus there is a need to provide binders for mineral wool which are produced at least partially from renewable materials.

[0008] Another effect associated with the previously known aqueous binder compositions for mineral fibres is that they involve corrosive and / or harmful components. This requires protective measures for the machinery involved in the production of mineral wool products against corrosion, and also safety measures for the personnel operating the machinery. This leads to increased costs and health problems, and thus there is a need to provide binder compositions for mineral fibres which have a reduced content of corrosive and / or harmful materials.

[0009] Recently, many binders for mineral fibres have been provided which are based to a large extent on renewable raw materials. In many cases, these binders based to a large extent on renewable resources also do not contain formaldehyde.

[0010] However, many of these binders are still relatively expensive because they are based on relatively expensive base materials.

[0011] At the same time, binders for mineral fibres have been provided which are based on a lignin component which has been oxidised to make it suitable as a component of a binder composition for mineral wool. Although very good binding properties are achieved by these mineral wool binders based on pre-oxidised lignin, the preparation of such binders still requires an additional step of oxidising the lignin component before it can be used as a component of a binder composition. This pre-oxidation step which is necessary with the lignin component complicates the production process of such binders to some extent because of the increased reaction time, reduced yield, and increases the costs of such binders because of the additional costs of raw materials, process equipment and personnel. SUMMARY

[0013] It is therefore an object of the present invention to provide binder compositions which are particularly suitable for binding mineral fibres, use renewable materials as starting materials, reduce or eliminate corrosive and / or harmful materials, and are inexpensive and fast to produce.

[0014] It is a further object of the present invention to provide mineral wool products bound with such binder compositions.

[0015] It is a further object of the present invention to provide a process for the preparation of such mineral wool products.

[0016] In addition, the present invention provides the use of a lignin component for the preparation of a binder composition for mineral wool.

[0017] According to a first aspect of the present application, there is provided an aqueous binder composition for mineral fibres having a pH of > 8, preferably free of phenol and formaldehyde, comprising:

[0018] - component (i) in the form of one or more sulphate lignins having a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin;

[0019] - component (ii) in the form of one or more cross-linking agents;

[0020] - component (iii) in the form of one or more plasticizers.

[0021] In particular, according to a first aspect of the present application, there is provided an aqueous binder composition for mineral fibres having a pH of > 8, preferably free of phenol and formaldehyde, comprising:

[0022] - component (i) in the form of one or more sulphate lignins having a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin;

[0023] - component (ii) in the form of one or more cross-linking agents;

[0024] - component (iii) in the form of one or more plasticizers,

[0025] with the proviso that the composition does not comprise a cross-linking agent selected from the group consisting of epoxide compounds having a molecular weight M W of 500 or less.

[0026] According to a second aspect of the present application, there is provided a method of producing a bound mineral fibre product, the method comprising the step of contacting mineral fibres with the aqueous binder composition described above.

[0027] According to a third aspect of the present application, there is provided a mineral wool product comprising mineral fibres in contact with the cured binder composition of the present application.

[0028] According to a fourth aspect of the present application, there is provided the use of a lignin component in the form of one or more sulphate lignins and having a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin, for the preparation of a binder composition for mineral wool.

[0029] In particular, according to the fourth aspect of the present application, there is provided the use of a lignin component in the form of one or more sulphate lignins having a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin, for the preparation of a binder composition for mineral wool, with the proviso that the composition does not comprise a crosslinker selected from the group consisting of epoxide compounds having a molecular weight M W

[0030] The present inventors have surprisingly found that a mineral wool product comprising mineral fibres bound by a binder resulting from the curing of a binder composition can be obtained, wherein the binder composition can largely be produced from inexpensive renewable material in the form of a lignin component which does not require an oxidation step prior to use in the binder composition and which binder composition does not contain or only to a small extent contains any corrosive and / or harmful agents.

[0031] Description of preferred embodiments

[0032] According to the first aspect of the present application, there is provided an aqueous binder composition for mineral fibres having a pH of > 8, preferably being free of phenol and formaldehyde, comprising:

[0033] - a component (i) in the form of one or more sulphate lignins having a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin;

[0034] - a component (ii) in the form of one or more crosslinkers;

[0035] - a component (iii) in the form of one or more plasticizers.

[0036] In particular, according to the first aspect of the present application, there is provided an aqueous binder composition for mineral fibres having a pH of > 8, preferably being free of phenol and formaldehyde, comprising:

[0037] - a component (i) in the form of one or more sulphate lignins having a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin;

[0038] - a component (ii) in the form of one or more crosslinkers;

[0039] - a component (iii) in the form of one or more plasticizers,

[0040] ​provided that the composition does not comprise a crosslinker selected from epoxide compounds having a molecular weight M W of 500 or less.

[0041] In a preferred embodiment, the binder of the present application is formaldehyde-free.

[0042] For the purpose of the present application, the term "formaldehyde-free" is defined as characterizing a mineral wool product, wherein the formaldehyde emission of the mineral wool product is below 5 pg / m 2 / h, preferably below 3 pg / m 2 / h. Preferably, the test is performed according to ISO 16000 for testing aldehyde emissions.

[0043] In a preferred embodiment, the binder of the present application is phenol-free.

[0044] For the purpose of the present application, the term "phenol-free" is defined as the aqueous binder composition contains phenol in an amount of < 0.25 wt%, such as < 0.1 wt%, such as < 0.05 wt%:

[0045]

[0046] based on the total weight of the aqueous composition having a dry solids binder content of 15 wt%.

[0047] In an embodiment, the binder composition does not contain added formaldehyde.

[0048] In an embodiment, the binder composition does not contain added phenol.

[0049] Component (i)

[0050] Component (i) is in the form of one or more sulphate lignins and has a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 2.0 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin.

[0051] Lignin, cellulose and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be considered as a glue that holds the cellulose fibres together. Lignin contains hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, second only to cellulose, and is estimated to constitute up to 20-30% of the total carbon contained in biomass, more than 1 billion tons globally.

[0052] Figure 1 A part of a possible lignin structure is shown.

[0053] The Kraft process introduces thiol groups, 1,2-diphenylethene, while retaining some carbohydrates. Sodium sulfate is also present as an impurity due to the precipitation of lignin from the liquor with sulfuric acid, but can potentially be avoided by changing the way lignin is isolated. The Kraft process results in a high number of phenolic hydroxyl groups and this lignin is soluble in water when these groups are ionized (at a pH higher than about 10).

[0054] The purity of commercial Kraft lignin is usually higher than that of lignosulfonates. The number average molecular weight is 800-6000 g / mol.

[0055] In one embodiment, component (i) has a carboxylic acid group content of 0.15 to 0.6 mmol / g, based on the dry weight of the Kraft lignin.

[0056] In one embodiment, component (i) is in the form of one or more Kraft lignins having an average carboxylic acid group content of less than 1.8 groups per macromolecule, such as less than 1.4 groups per macromolecule, such as less than 1.1 groups per macromolecule, such as less than 0.7 groups per macromolecule, taking into account the number average molecular weight of component (i).

[0057] In one embodiment, component (i) has a nitrogen content of < 1.2 wt%, such as < 0.5 wt%, such as < 0.3 wt%, based on the dry weight of component (i).

[0058] In one embodiment, component (i) has a phenolic hydroxyl group content of 2.0 to 5.0 mmol / g, such as 2.0 to 4.0 mmol / g, such as 2.5 to 3.5 mmol / g, based on the dry weight of the Kraft lignin.

[0059] In one embodiment, component (i) has an aliphatic hydroxyl group content of 0.7 to 3.0 mmol / g, such as 0.7 to 2.5 mmol / g, such as 1.0 to 2.0 mmol / g, based on the dry weight of the Kraft lignin.

[0060] In one embodiment, the aqueous binder composition comprises component (i) in an amount of 50 to 98 wt%, such as 65 to 98 wt%, such as 80 to 98 wt%, based on the dry weight of components (i), (ii) and (iii).

[0061] For the purposes of the present application, the content of lignin functional groups is determined by using 31 P NMR as a characterization method.

[0062] For the purposes of the present application, the content of lignin functional groups is determined by using 31Sample preparation for P NMR was performed by using 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) as a phosphitylating reagent and using cholestanol as an internal standard. Integration was performed according to the work of Granata and Argyropoulos (J. Agric. Food Chem. 43: 1538-1544).

[0063] For the purposes of the present invention, the number average molecular weight is determined by using a UV detector at a wavelength of 280 nm with 0.1 M NaOH as eluent and a set of polystyrene sulfonate standards.

[0064] Component (ii)

[0065] Component (ii) is in the form of one or more crosslinking agents.

[0066] In one embodiment, the component (ii) comprises one or more crosslinking agents selected from the group consisting of beta-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

[0067] Beta-hydroxyalkylamide crosslinking agents are curing agents for acid-functional macromolecules. They provide a hard, durable, corrosion-resistant and solvent-resistant crosslinked polymer network. It is believed that beta-hydroxyalkylamide crosslinking agents cure by esterification reactions to form multiple ester linkages. The hydroxyl functionality of the beta-hydroxyalkylamide crosslinking agents should average at least 2, preferably greater than 2, more preferably 2-4, for optimum curing response.

[0068] Oxazoline group-containing crosslinking agents are polymers containing one or more oxazoline groups in each molecule, and typically oxazoline-containing crosslinking agents can be readily obtained by polymerization of oxazoline derivatives. Patent US6818699 B2 provides a disclosure on such a process.

[0069] In one embodiment, component (ii) is one or more crosslinking agents selected from the group consisting of multifunctional organic amines, such as alkanolamines, diamines such as 1,6-hexanediamine.

[0070] In one embodiment, the component (ii) is one or more epoxy compounds having a molecular weight exceeding 500, such as epoxidized oils based on fatty acid triglycerides, or one or more flexible oligomers or polymers, such as low Tg acrylic-based polymers, such as low Tg vinyl polymers, such as low Tg polyethers, containing reactive functional groups, such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups, such as beta-hydroxyalkylamide groups.

[0071] In one embodiment, component (ii) is one or more crosslinking agents selected from the group of polyethylene imines, polyvinyl amines, fatty amines.

[0072] In one embodiment, component (ii) is one or more crosslinking agents in the form of fatty amides.

[0073] In one embodiment, component (ii) is one or more crosslinking agents selected from the group of dimethoxy acetaldehyde, glycolic aldehyde, glyoxylic acid.

[0074] In one embodiment, component (ii) is one or more crosslinking agents selected from polyesters polyols such as polycaprolactone.

[0075] In one embodiment, component (ii) is one or more crosslinking agents selected from the group of starch, modified starch, CMC.

[0076] In one embodiment, component (ii) is one or more crosslinking agents in the form of a multifunctional carbodiimide such as an aliphatic multifunctional carbodiimide.

[0077] In one embodiment, the component (ii) is one or more crosslinking agents in the form of aziridines, such as CX100, NeoAdd-Pax 521 / 523.

[0078] In one embodiment, component (ii) is one or more crosslinking agents selected from melamine based crosslinking agents such as hexa(methylmethoxy)melamine (HMMM) based crosslinking agents.

[0079] Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), such as XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).

[0080] In one embodiment, component (ii) is Primid XL552, which has the following structure:

[0081]

[0082] Component (ii) can also be any mixture of the above mentioned compounds.

[0083] In one embodiment, the binder composition of the present application comprises component (ii) in an amount of 1 to 50 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of component (i).

[0084] Component (iii) of the binder composition

[0085] Optionally and preferably, the binder composition can comprise component (iii). Component (iii) is in the form of one or more plasticizers.

[0086] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyglycol ethers, polyethers, phthalates and / or other esters, such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic based polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides such as urea / urethanes, or any mixture thereof.

[0087] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with structures similar to lignin such as vanillin, acetyl vanillin, solvents used as coalescing agents such as alcohol ethers, polyvinyl alcohol.

[0088] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from the group consisting of polyethylene glycol, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or other esters, solvents used as coalescing agents such as alcohol ethers, acrylic polymers, polyvinyl alcohol.

[0089] In one embodiment, component (iii) is one or more reactive plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tri-carboxylic acids, such as adipic acid, or lactic acid, and / or vanillic acid and / or ferulic acid, polyurethane dispersions, acrylic based polymers with free carboxyl groups, compounds with structures similar to lignin such as vanillin, acetyl vanillin.

[0090] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.

[0091] In one embodiment, component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycol, polyethylene glycol ethers, and / or triethanolamine.

[0092] Another particularly surprising aspect of the present invention is that the use of plasticizers having a boiling point of more than 100°C, in particular a boiling point of 140 to 320°C, greatly improves the mechanical properties of the mineral fiber product of the present invention, although these plasticizers are likely to evaporate at least partially during the binder curing process in contact with the mineral fibers, given their boiling point.

[0093] In one embodiment, component (iii) comprises one or more plasticizers having a boiling point of more than 100°C, for example 100 to 380°C, for example 110 to 350°C, more preferably 120 to 300°C, more preferably 140 to 250°C.

[0094] It is believed that the effectiveness of these plasticizers in the binder composition of the present invention is related to the effect of increasing the flowability of the lignin during the curing process. It is believed that the increased flowability of the lignin during the curing process facilitates effective cross-linking. It is also believed that the presence of the plasticizer prevents loss of adhesion to the fibers during the initial stages of curing by keeping the lignin in a rubbery state (above its T g ).

[0095] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50 000 g / mol, in particular 150 to 4000 g / mol, more particularly 150 to 1000 g / mol, preferably 150 to 500 g / mol, more preferably 200 to 400 g / mol.

[0096] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4000 to 25 000 g / mol, in particular 4000 to 15 000 g / mol, more particularly 8000 to 12 000 g / mol.

[0097] In one embodiment, component (iii) is capable of forming covalent bonds with component (i) and / or component (ii) during the curing process. Such components will not evaporate and remain as part of the composition, but will be effectively altered so as not to introduce unwanted side effects such as water absorption of the cured product. Non-limiting examples of such components are caprolactone and acrylic based polymers having free carboxylic groups.

[0098] In one embodiment, component (iii) is selected from the group consisting of fatty alcohols, monohydroxy alcohols, for example pentanol, stearyl alcohol.

[0099] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxylates, for example ethoxylates, for example butanol ethoxylates such as butoxylated triethylene glycol.

[0100] In one embodiment, component (iii) is selected from one or more glycols.

[0101] In one embodiment, component (iii) is selected from one or more diol esters.

[0102] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of adipate esters, acetate esters, benzoate esters, cyclohexanoate esters, citrate esters, stearate esters, sorbate esters, sebacate esters, azelate esters, butyrate esters, valerate esters.

[0103] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of phenol derivatives, such as alkyl or aryl substituted phenols.

[0104] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of silanols, siloxanes.

[0105] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of sulphate esters such as alkyl sulphate esters, sulphonate esters such as alkyl aryl sulphonate esters, for example alkyl sulphonate esters, phosphate esters such as tri-polyphosphate esters; for example tributyl phosphate.

[0106] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0107] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of monomeric amides, for example acetamides, benzamides, fatty acid amides, for example tall oil amides.

[0108] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds, for example trimethyl glycine, distearyl dimethyl ammonium chloride.

[0109] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of vegetable oils, for example castor oil, palm oil, linseed oil, tall oil, soybean oil.

[0110] In one embodiment, component (iii) is in the form of tall oil.

[0111] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils.

[0112] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0113] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucosides, glucoamides, aminoglucose amides, sucrose esters, sorbitol esters.

[0114] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers.

[0115] In one embodiment, component (iii) is selected from one or more plasticizers in the form of a polyol such as glycerol, 1,1,1 -tris(hydroxymethyl)propane.

[0116] In one embodiment, component (iii) is triethanolamine.

[0117] In one embodiment, component (iii) is in the form of propylene glycol, phenol derivatives, silanols, siloxanes, hydroxy acids, vegetable oils, polyethylene glycols, polyethylene glycol ethers, triethanolamine or any mixture thereof.

[0118] It has surprisingly been found that the inclusion of a plasticizer in the binder composition of the present invention greatly improves the mechanical properties of the mineral fiber product of the present invention.

[0119] The term "plasticizer" means a substance added to a material to make it softer, more flexible (by lowering the glass transition temperature Tg) and easier to process.

[0120] Component (iii) can also be any mixture of the above mentioned compounds.

[0121] In one embodiment, component (iii) is present in an amount of 0.5 to 60 wt.-%, preferably 2.5 to 25 wt.-%, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).

[0122] In one embodiment, component (iii) is present in an amount of 0.5 to 60 wt.-%, preferably 2.5 to 25 wt.-%, more preferably 3 to 15 wt.-%, based on the dry weight of components (i), (ii) and (iii).

[0123] Binder composition for mineral fibers comprising components (i) and (iia)

[0124] In one embodiment, the present invention relates to a binder composition for mineral fibers, comprising:

[0125] - component (i) in the form of one or more sulphate lignins having a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 2.0 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin;

[0126] - component (iia) in the form of one or more modifiers,

[0127] Preferably, provided that the composition does not comprise a crosslinking agent selected from epoxide compounds having a molecular weight M W of 500 or less.

[0128] The present inventors have found that excellent binder performance can also be achieved by a two-component system comprising: component (i) in the form of one or more sulphate lignins having a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 2.0 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin; and component (iia) in the form of one or more modifiers; and optionally any of the other components mentioned above and below.

[0129] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from the group of epoxide compounds having a molecular weight greater than 500, such as epoxidized oils based on fatty acid triglycerides, or one or more flexible oligomers or polymers, such as low Tg acrylic based polymers, such as low Tg vinyl polymers, such as low Tg polyethers, containing reactive functional groups, such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups, such as beta-hydroxyalkylamide groups.

[0130] In one embodiment, component (iia) is one or more modifiers selected from the group of polyethyleneimines, polyvinyl amines, fatty amines.

[0131] In one embodiment, component (iia) is one or more modifiers selected from the group of aliphatic multifunctional carbodiimides.

[0132] Component (iia) can also be any mixture of the compounds mentioned above.

[0133] Without wishing to be bound by any particular theory, the present inventors believe that the excellent binder performance achieved by the mineral fibre binder composition comprising components (i) and (iia) and optionally additional components is at least in part due to the effect of the modifier used as component (iia) at least in part functioning as a plasticizer and a crosslinking agent.

[0134] In one embodiment, the binder composition comprises component (iia) in an amount of 1 to 60 wt.%, such as 4 to 20 wt.%, such as 6 to 12 wt.%, based on the dry weight of component (i).

[0135] Further components

[0136] In some embodiments, the adhesive composition of the present application comprises further components.

[0137] In one embodiment, the adhesive composition of the present application comprises a catalyst selected from the group consisting of inorganic acids, such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid and / or phosphoric acid, and / or any salts thereof, such as sodium hypophosphite, and / or ammonium salts such as ammonium salts of sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid and / or phosphoric acid, and / or sodium polyphosphate (STTP), and / or sodium trimetaphosphate (STMP), and / or phosphorous oxychloride. The presence of such catalysts can improve the curing properties of the adhesive composition of the present application.

[0138] In one embodiment, the adhesive composition of the present application comprises a catalyst selected from Lewis acids which can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCI2, Mg(CIO4)2, Sn[N(SO2-n-C8F 17 )2]4.

[0139] In one embodiment, the adhesive composition of the present application comprises a catalyst selected from metal chlorides, such as KCI, MgCI2, ZnCI2, FeCI3and SnCI2, or adducts thereof, such as AlCI3adducts, such as BF3adducts, such as BF3-ethylamine complex.

[0140] In one embodiment, the adhesive composition of the present application comprises a catalyst selected from metal organic compounds, such as titanate-based catalysts and tin-based catalysts.

[0141] In one embodiment, the adhesive composition of the present application comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions, and / or selected from peroxides such as organic peroxides, such as dicumyl peroxide.

[0142] In one embodiment, the adhesive composition of the present application comprises a catalyst selected from phosphites such as alkyl phosphites, aryl phosphites such as triphenyl phosphite.

[0143] In one embodiment, the adhesive composition of the present application comprises a catalyst selected from tertiary amines such as tri-2,4,6-dimethylaminomethylphenol.

[0144] In one embodiment, the adhesive composition of the present application further comprises a further component (iv) in the form of one or more silanes.

[0145] In one embodiment, component (iv) is in the form of one or more coupling agents such as organofunctional silanes.

[0146] In one embodiment, component (iv) is selected from organofunctional silanes, such as primary or secondary amino-functionalized silanes, epoxy-functionalized silanes such as polymeric or oligomeric epoxy-functionalized silanes, methacrylate-functionalized silanes, alkyl and aryl-functionalized silanes, urea-functionalized silanes or vinyl-functionalized silanes.

[0147] In one embodiment, the binder composition of the present application further comprises component (v) in the form of one or more components selected from the group consisting of bases, such as ammonia, alkali metal hydroxides such as KOH, alkaline earth metal hydroxides such as Ca(OH)2, Mg(OH)2, amines or any salts thereof.

[0148] In one embodiment, the binder composition of the present application further comprises an additional component in the form of urea, in particular in an amount of 5 to 40 wt%, such as 10 to 30 wt%, 15 to 25 wt%, based on the dry weight of component (i).

[0149] In one embodiment, the binder composition of the present application comprises an additional component (vi) in the form of one or more reactive or non-reactive organosilicon.

[0150] In one embodiment, said component (vi) is selected from the group consisting of organosilicon consisting of a backbone composed of organosiloxane residues, in particular diphenylsiloxane residues, alkylsiloxane residues, preferably dimethylsiloxane residues, which carry at least one hydroxyl, carboxyl or anhydride, amine, epoxy or vinyl functional group capable of reacting with at least one component of the binder composition, and said component (vi) is preferably present in an amount of 0.025 to 15 wt%, preferably 0.1 to 10 wt%, more preferably 0.3 to 8 wt%, based on the binder solids.

[0151] In one embodiment, the binder composition of the present application does not contain ammonium oxidized lignin (AOL).

[0152] In one embodiment, the binder composition of the present application further comprises an additional component in the form of one or more hydrocarbon oils.

[0153] In one embodiment, the binder composition of the present application further comprises an additional component in the form of one or more carbohydrates selected from the group consisting of sucrose, reducing sugars, in particular dextrose, polysaccharides, and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, more preferably glucose syrup having a dextrose equivalent value DE of 30 to less than 100, for example DE of 60 to less than 100, for example DE = 60-99, for example DE = 85-99, for example DE = 95-99.

[0154] In one embodiment, the binder composition of the present application further comprises an additional component in the form of one or more carbohydrates selected from sucrose and reducing sugars in an amount of 5 to 50 wt.-%, for example 5 to less than 50 wt.-%, for example 10-40 wt.-%, for example 15-30 wt.-%, based on the dry weight of component (i).

[0155] In the context of the present application, a binder composition having a sugar content of 50 wt.-% or more, based on the total dry weight of the binder components, is considered to be a sugar-based binder. In the context of the present application, a binder composition having a sugar content of less than 50 wt.-%, based on the total dry weight of the binder components, is considered to be a non-sugar-based binder.

[0156] In one embodiment, the binder composition of the present application further comprises an additional component in the form of one or more surfactants in the form of non-ionic and / or ionic emulsifiers, for example polyoxyethylene (4) lauryl ether, soy lecithin, sodium dodecyl sulfate.

[0157] In one embodiment, the aqueous binder composition of the present application consists essentially of the following components:

[0158] - component (i) in the form of one or more lignins selected from the group consisting of kraft lignin having a carboxylic acid group content of 0.03 to 2.0 mmol / g, for example 0.03 to 0.9 mmol / g, for example 0.15 to 2.0 mmol / g, for example 0.15 to 0.9 mmol / g, based on the dry weight of the kraft lignin, and / or

[0159] - component (ii) in the form of one or more crosslinking agents;

[0160] - component (iii) in the form of one or more plasticizers;

[0161] - component (iv) in the form of one or more coupling agents, such as organofunctional silanes;

[0162] - optional components in the form of one or more compounds selected from the group consisting of bases, such as ammonia, alkali metal hydroxides, such as KOH, alkaline earth metal hydroxides, such as Ca(OH)2, Mg(OH)2, amines or any salts thereof;

[0163] - optional components in the form of urea;

[0164] - optional components in the form of one or more reactive or non-reactive silicones;

[0165] - optionally one or more hydrocarbon oils;

[0166] - optionally one or more surfactants;

[0167] - water.

[0168] Method of producing a mineral fibre product

[0169] The present invention also provides a method of producing a mineral fibre product by bonding mineral fibres with the binder composition.

[0170] The present invention thus also relates to a method of producing a mineral fibre product, the method comprising the step of contacting mineral fibres with a binder composition, said binder composition comprising:

[0171] - component (i) in the form of one or more sulphate lignins and / or alkali lignins having a carboxylic acid group content of 0.03 to 2.0 mmol / g, such as 0.03 to 0.9 mmol / g, such as 0.15 to 2.0 mmol / g, such as 0.15 to 0.9 mmol / g, based on the dry weight of the sulphate lignin and / or alkali lignin;

[0172] - component (ii) in the form of one or more cross-linking agents;

[0173] - component (iii) in the form of one or more plasticizers,

[0174] Preferably, provided that the composition does not comprise a cross-linking agent selected from the group of epoxide compounds having a molecular weight M W of 500 or less.

[0175] Curing

[0176] The web is cured by chemical and / or physical reaction of the binder components.

[0177] In one embodiment, the curing is performed in a curing device.

[0178] In one embodiment, the curing is performed at a temperature of 100-300°C, such as 170-270°C, such as 180-250°C, such as 190-230°C.

[0179] In one embodiment, the curing is performed in a conventional curing oven used for mineral wool production, which is operated at a temperature of 150 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.

[0180] In one embodiment, the curing is performed for a time period of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.

[0181] In one typical embodiment, the curing is performed at a temperature of 150 to 250°C for a time period of 30 seconds to 20 minutes.

[0182] The curing process can be initiated immediately after the binder is applied to the fibres. Curing is defined as the process by which the binder composition undergoes physical and / or chemical reactions (in the case of chemical reactions curing typically increases the molecular weight of the compounds in the binder composition) and thereby increases the viscosity of the binder composition, typically until the binder composition reaches a solid state.

[0183] In one embodiment, the curing of the binder in contact with the mineral fibres is performed in a hot press.

[0184] Curing the binder in contact with the mineral fibres in a hot press has the particular advantage that it enables the production of high density products.

[0185] In one embodiment, the curing process comprises drying by pressure. The pressure can be applied by blowing air or gas through / over the mixture of mineral fibres and binder.

[0186] Mineral fibre product of the invention

[0187] The present invention also relates to a mineral fibre product comprising mineral fibres in contact with the cured binder composition described above (i.e. in contact with the cured binder resulting from the curing of the aqueous binder composition described above).

[0188] The mineral fibres employed can be any of man-made vitreous fibres (MMVF), glass fibres, ceramic fibres, basalt fibres, slag fibres, rock fibres, stone fibres etc. The fibres can be present in the form of a batt product such as an asbestos product.

[0189] Fibre / melt composition

[0190] The man-made vitreous fibres (MMVF) can have any suitable oxide composition. The fibres can be glass fibres, ceramic fibres, basalt fibres, slag fibres, or rock or stone fibres. The fibres are preferably of the type commonly known as rock, stone or slag fibres, most preferably stone fibres.

[0191] The stone fibres typically comprise the following oxides, expressed in weight percent:

[0192] SiO2: 30-51

[0193] CaO: 8-30

[0194] MgO: 2-25

[0195] FeO (including Fe2O3): 2-15

[0196] Na2O + K2O: not more than 10

[0197] CaO + MgO: 10-30

[0198] In some preferred embodiments, the MMVF have the following element levels, calculated as oxides and expressed in weight %:

[0199] SiO2: at least 30, 32, 35 or 37; not more than 51, 48, 45 or 43

[0200] Al2O3: at least 12, 16 or 17; not more than 30, 27 or 25

[0201] CaO: at least 8 or 10; not more than 30, 25 or 20

[0202] MgO: at least 2 or 5; not more than 25, 20 or 15

[0203] FeO (including Fe2O3): at least 4 or 5; not more than 15, 12 or 10

[0204] FeO + MgO: at least 10, 12 or 15; not more than 30, 25 or 20

[0205] Na2O + K2O: 0 or at least 1; not more than 10

[0206] CaO + MgO: at least 10 or 15; not more than 30 or 25

[0207] TiO2: 0 or at least 1; not more than 6, 4 or 2

[0208] TiO2 + FeO: at least 4 or 6; not more than 18 or 12

[0209] B203: 0 or at least 1 ; not more than 5 or 3

[0210] P205: 0 or at least 1 ; not more than 8 or 5

[0211] Other: 0 or at least 1 ; not more than 8 or 5

[0212] The MMVF produced by the process of the present application preferably has the following composition (in wt%):

[0213] Si02: 35 - 50

[0214] Al203: 12 - 30

[0215] Ti02: at most 2

[0216] Fe203: 3 - 12

[0217] CaO: 5 - 30

[0218] MgO: at most 15

[0219] Na20: 0 - 15

[0220] K20: 0 - 15

[0221] P205: at most 3

[0222] MnO: at most 3

[0223] B203: at most 3

[0224] Another preferred composition of the MMVF is as follows (in wt%):

[0225] Si02: 39 - 55%, preferably 39 - 52%

[0226] Al203: 16 - 27%, preferably 16 - 26%

[0227] CaO: 6 - 20%, preferably 8 - 18%

[0228] MgO: 1 - 5%, preferably 1 - 4.9%

[0229] Na20: 0 - 15%, preferably 2 - 12%

[0230] K20: 0 - 15%, preferably 2 - 12%

[0231] R20 (Na20 + K20): 10 - 14.7%, preferably 10 - 13.5%

[0232] P205: 0 - 3%, preferably 0 - 2%

[0233] Fe203(total iron): 3-15%, preferably 3.2-8%

[0234] B203: 0-2%, preferably 0-1%

[0235] Ti02: 0-2%, preferably 0.4-1%

[0236] Others: 0-2.0%

[0237] Glass fibres typically comprise the following oxides (in wt%):

[0238] Si02: 50-70

[0239] Al203: 10-30

[0240] CaO: not more than 27

[0241] MgO: not more than 12

[0242] Glass fibres can also contain the following oxides (in wt%):

[0243] Na20 + K20: 8-18, in particular Na20 + K20 is greater than CaO + MgO

[0244] B203: 3-12

[0245] Certain glass fibre compositions can contain less than 2% Al203.

[0246] Suitable fibre forming processes and subsequent production steps for making mineral fibre products are those conventional in the art. Typically, the binder is sprayed onto the airborne mineral fibres immediately after the mineral melt is fibrillated. The aqueous binder composition is typically applied in an amount of 0.1 to 18 wt%, preferably 0.2 to 8 wt%, based on dry weight, of the bonded mineral fibre product.

[0247] The sprayed mineral fibre web is typically cured in a curing oven using a hot air stream. The hot air stream can be introduced into the mineral fibre web from below or from above or from alternating directions in different zones along the length of the curing oven.

[0248] Typically, the curing oven is operated at a temperature of from about 150°C to about 300°C, for example 170 to 270°C, for example 180 to 250°C, for example 190 to 230°C. Typically, the curing oven residence time is from 30 seconds to 20 minutes, for example 1 to 15 minutes, for example 2 to 10 minutes, depending on, for example, the product density.

[0249] In one typical embodiment, the mineral fibre product of the present application is cured at a temperature of from 150°C to 250°C for a time of from 30 seconds to 20 minutes.

[0250] If desired, the mineral wool web can be subjected to a forming treatment prior to curing. The bonded mineral fibre product coming out of the curing oven can be cut into the desired form, for example in the form of batts. Thus, the mineral fibre product produced has the form of, for example, woven and non-woven fabrics, mats, batts, slabs, sheets, boards, strips, rolls, granules and other shaped articles, which can be used, for example, as thermal or acoustic insulation, as a vibration dampening, as a building material, as a reinforcing material for external wall insulation, roof or floor applications, as filter stock for motor oil and other applications.

[0251] According to the application, it is also possible to produce composite materials by combining the bonded mineral fibre product with suitable composite or laminated layers, such as metal, glass surface mats and other woven or non-woven materials.

[0252] The mineral fibre product of the application typically has a density in the range of 6 to 250 kg / m3 3 , preferably 20 to 200 kg / m3 3 . The mineral fibre product typically has a loss on ignition (LOI) in the range of 0.3 to 18.0 %, preferably 0.5 to 8.0 %.

[0253] Although the aqueous binder composition of the application is particularly suitable for bonding mineral fibres, it can likewise be used in other applications typical for binders and sizing agents, for example as a binder for foundry sand, glass fibre tissue, composites, mouldings, coatings, for example as a metal adhesive.

[0254] In an alternative embodiment, the binder described above can also be a binder for products other than mineral wool products. In one embodiment, the binder composition described above is a binder composition for bonding wood products.

[0255] The application therefore also relates to a binder composition, in particular a binder composition for wood products, comprising components (i), (ii) and (iii), preferably having the above defined preconditions.

[0256] Use of a lignin component for the preparation of a binder composition

[0257] The application also relates to the use of a lignin component for the preparation of a binder composition for mineral wool, the lignin component being in the form of one or more sulphate lignins and having the features described above for component (i).

[0258] In one embodiment, the binder composition is free of phenol and formaldehyde.

[0259] In one embodiment, the present application relates to the use of a lignin component for the preparation of a binder composition for mineral wool, preferably free of phenol and formaldehyde, said lignin component being in the form of one or more sulphate lignins and having the features of component (i) described above, wherein the binder composition further comprises components (ii) and (iii) as defined above, preferably with the proviso that the composition does not comprise a crosslinker selected from epoxide compounds having a molecular weight MW of 500 or less.

[0260] In one embodiment, the present application relates to the use of a lignin component for the preparation of a binder composition, said lignin component being in the form of one or more sulphate lignins and having the features of component (i) described above, wherein the binder composition further comprises component (iia) as defined above.

[0261] The present application also relates to the use of a lignin component for the preparation of a binder composition for wood products, said lignin component being in the form of one or more sulphate lignins and having the features described above for component (i).

[0262] In one embodiment, the binder composition is free of phenol and formaldehyde.

[0263] In one embodiment, the present application relates to the use of a lignin component for the preparation of a binder composition for wood products, preferably free of phenol and formaldehyde, said lignin component being in the form of one or more sulphate lignins and having the features of component (i) described above, wherein the binder composition further comprises components (ii) and (iii) as defined above, preferably with the proviso that the composition does not comprise a crosslinker selected from epoxide compounds having a molecular weight MW of 500 or less.

[0264] In one embodiment, the present application relates to the use of a lignin component for the preparation of a binder composition, said lignin component being in the form of one or more sulphate lignins and having the features of component (i) described above, wherein the binder composition further comprises component (iia) as defined above. Example

[0265] Example A - Laboratory tests

[0266] In the following examples, several binders falling within the definition of the present application were prepared and compared with prior art binders.

[0267] The following properties were determined for the binders of the present application and the prior art binders, respectively:

[0268] Binder component solids content

[0269] The content of each component in a given pre-cured binder solution is based on the anhydrous mass of the component.

[0270] Sulphate lignin was supplied by UPM as BioPivalOO TM Dry powders. Primid XL552 was supplied by EMS-CHEMIE AG, silane (Momentive VS-142 40% activity) was supplied by Momentive and was calculated as 100% for simplicity. 24.7% NH4OH was supplied by Univar and used as supplied. PEG 200, urea, KOH pellets, 1,1,1-tris(hydroxymethyl)propane were supplied by Sigma-Aldrich and were assumed to be anhydrous for simplicity.

[0271] Binder solids content

[0272] The content of the binder after curing is referred to as the "binder solids content".

[0273] A disc shaped asbestos sample (diameter 5 cm; height 1 cm) was cut from asbestos and heat treated at 580°C for at least 30 minutes to remove all organic matter. The solids content of a binder mixture was measured by distributing a sample (approximately 2 g) of the binder mixture onto a heat treated asbestos disc in a tin foil container. The weight of the tin foil container containing the asbestos disc was weighed before and immediately after addition of the binder mixture. Two such asbestos discs loaded with binder mixture in a tin foil container were produced and then heated at 200°C for 1 hour. After cooling and storage at room temperature for 10 minutes, the samples were weighed and the binder solids content was calculated as the average of the two results.

[0274] A binder with the desired binder solids content can then be produced by dilution with the required amount of water and a 10% aqueous solution of silane (Momentive VS-142).

[0275] Mechanical strength study

[0276] Strip test

[0277] The mechanical strength of the binders was tested in a strip test. For each binder, 16 strips were made from a mixture of binder and asbestos balls from asbestos spinning production.

[0278] A sample of binder solution with a dry solids content of 15% (16.0 g) was thoroughly mixed with asbestos balls (80.0 g). The resulting mixture was then filled into four grooves of a heat-resistant silicone mould to produce small strips (4 x 5 grooves per mould; groove top dimensions: length = 5.6 cm, width = 2.5 cm; groove bottom dimensions: length = 5.3 cm, width = 2.2 cm; groove height = 1.1 cm). The mixture placed in the grooves was then pressed with a flat metal bar of appropriate dimensions to produce a flat strip surface. In this way 16 strips were produced from each binder. The resulting strips were then cured, typically at 225°C. The curing time was 1 hour. After cooling to room temperature, the strips were carefully removed from the container. Five of the strips were aged in a water bath at 80°C for 3 hours.

[0279] After drying for 3 days, the aged strips and 5 unaged strips were broken in a 3-point bending test on a Bent Tram machine (test speed: 10.0 mm / min; break level: 50%; nominal strength: 30 N / mm 2 ; support distance: 40 mm; maximum deviation: 20 mm; nominal e-modulus: 10000 N / mm 2 ) to investigate their mechanical strength. The strips were placed in the machine with the "top face" (i.e. the face with dimensions length = 5.6 cm, width = 2.5 cm) facing upwards.

[0280] Binder Example, Reference Binder (phenol-formaldehyde resin modified with urea PUF-resol)

[0281] This binder is a phenol-formaldehyde resin modified with urea PUF-resol.

[0282] A phenol-formaldehyde resin was prepared by reacting a 37% aqueous formaldehyde solution (606 g) and phenol (189 g) in the presence of a 46% aqueous potassium hydroxide solution (25.5 g) at a reaction temperature of 84°C with a heating rate of approximately 1 °C / min to the reaction temperature. The reaction was continued at 84°C until the acid tolerance of the resin was 4 and most of the phenol was converted. Then urea (241 g) was added and the mixture was cooled.

[0283] The acid tolerance (AT) indicates the factor by which a given volume of binder can be diluted with acid without the mixture becoming turbid (the binder precipitates). Sulfuric acid is used to determine the stop criterion in the production of the binder and an acid tolerance below 4 indicates that the binder reaction is finished.

[0284] To measure AT, a titrant is prepared by diluting 2.5 ml of concentrated sulphuric acid (>99%) with 1 L of ion exchange water. Then 5 millilitres of the binder under study is titrated with the titrant at room temperature while keeping the binder in motion by hand shaking; if desired, a magnetic stirrer and a magnetic bar can be used. The titration is continued until a slight haze appears in the binder, which does not disappear when the binder is shaken.

[0285] The acid tolerance (AT) is calculated by dividing the amount of acid used for the titration (mL) by the amount of sample (mL):

[0286] AT = (volume of titrant used (mL)) / (volume of sample (mL))

[0287] Using the obtained urea-modified phenol-formaldehyde resin, a binder is prepared by adding 25% ammonia water (90 mL) and ammonium sulphate (13.2 g), followed by water (1.30 kg).

[0288] The binder solids content is then measured as described above and the mixture is diluted with the required amount of water and silane (15% binder solids content solution, 0.5% silane of the binder solids) for mechanical measurements.

[0289] Binder examples, reference binder (lignin based binder on alkali metal oxide)

[0290] In a 6000 litre reactor, 3267 kg of water is added, followed by 287 kg of ammonia water (24.7%). Then, 1531 kg of lignin UPM BioPiva 100 is slowly added over a period of 30 to 45 minutes. The mixture is heated to 40 °C and kept at this temperature for 1 hour. After 1 hour, the undissolved lignin is checked. This can be done by checking the solution on a glass plate or on a Hegman gauge. Undissolved lignin can be seen as small particles in the brownish binder. The colour of the lignin solution changes from brown to bright black during the dissolution step. After the lignin is completely dissolved, 1 litre of antifoam (available from of 11-10) is added. The batch temperature is kept at 40 °C. Then the addition of 307.5 kg of 35% hydrogen peroxide is started. The hydrogen peroxide is added at a rate of 200-300 litres / hour. The first half of the hydrogen peroxide is added at a rate of 200 litres / hour, after which the rate is increased to 300 litres / hour.

[0291] During the addition of the hydrogen peroxide, the temperature of the reaction mixture is controlled by heating or cooling to reach a final reaction temperature of 65 °C.

[0292] The final product is analysed for COOH group content, dry solids content, pH, viscosity and residual H2O2.

[0293] 60 g of this oxidized lignin (18.2% solids) was mixed with 1.4 g Primid XL552 (100% solids) and 2.8 g PEG200 (100% solids). 0.6 g silane (Momentive VS-142 40% activity, 10% concentration in water) and 17.4 g water were added and mixed to yield 15% solids and then used to test mechanical properties in strip tests.

[0294] Binder composition of the invention

[0295] In the following, the item numbers of the binder examples correspond to the item numbers used in Tables 1-1 to 1-4.

[0296] The following procedure was employed to dissolve kraft lignin in 21 vessels. 645 ml water and 100 ml NH4OH (24.7%) were mixed and then 255 g lignin (BioPival 00 TM ) was slowly added under stirring over 5 minutes. The mixture was stirred for two hours at 60°C. The kraft lignin prepared in this way was used in the following examples.

[0297] A portion of the solution was also freeze-dried and used 31 for P NMR characterization. The distribution of functional groups is shown in Table 1 and Figure 2 Figure 2 The P NMR spectrum of kraft lignin dissolved in ammonia and freeze-dried is shown. 31

[0298] Table 1

[0299]

[0300] Example 6

[0301] To 60.0 g kraft lignin solution (15.9% solids) was added 2.9 g Primid XL552 (100% solids) and mixed with 0.6 g silane (Momentive VS-142 40% activity, 10% concentration in water) and 19 g water to yield 15% solids and then used to test mechanical properties in strip tests.

[0302] Example 12

[0303] ​​To 60.0 g Kraft lignin solution (15.9% solids) was added 2.1 g Primid XL552 (100% solids) and 2.5 g PEG200 (100% solids) and mixed with 0.6 g Silane (Momentive VS-142 40% activity, 10% concentration in water) and 12.3 g water to make 15% solids and then used to test mechanical properties in strip testing.

[0304] Example 18

[0305] To 60.0 g Kraft lignin solution (15.9% solids) was added 2.1 g Primid XL552 (100% solids) and 2.5 g PEG200 (100% solids) and mixed with 0.6 g Silane (Momentive VS-142 40% activity, 10% concentration in water) and 12.3 g water to make 15% solids and then used to test mechanical properties in strip testing.

[0306] Example 24

[0307] To 60.0 g Kraft lignin solution (15.9% solids) was added 2.9 g 1,1,1- Tris(hydroxymethyl)propane (100% solids) and mixed with 0.8 g water to make 15% solids and then used to test mechanical properties in strip testing.

[0308] Example 28

[0309] To 60.0 g Kraft lignin solution (15.9% solids) was added 1.7 g Primid XL552 (100% solids) and 2.9 g 1,1,1- Tris(hydroxymethyl)propane (100% solids) and mixed with 0.6 g Silane (Momentive VS-142 40% activity, 10% concentration in water) and 9.3 g water to make 15% solids and then used to test mechanical properties in strip testing.

[0310] Example 30

[0311] To 60.0 g Kraft lignin solution (15.9% solids) was added 1.7 g Primid XL552 (100% solids), 1.3 g PEG200 (100 solids) and 1.3 g Urea (100% solids) and mixed with 0.6 g Silane (Momentive VS-142 40% activity, 10% concentration in water) and 10.1 g water to make 15% solids and then used to test mechanical properties in strip testing.

[0312] The mechanical properties are listed in Tables 1.1-1.4. For simplicity, all other component amounts are recalculated based on 100 g of dry lignin powder.

[0313] As can be seen from Table 1.1, a combination of crosslinker (Primid XL 552) and plasticizer (PEG 200) is needed to achieve high mechanical properties (strength in strip test, unaged and aged) as good or better than the reference binder (13, 15, 18 vs. 4 and 9 vs. reference binder).

[0314] Table 1.2 shows that different plasticizers (15 vs. 28) or combinations of plasticizers (28 vs. 30) can be used and that PEG 200 is the preferred plasticizer.

[0315] Table 1.3 shows that the addition of silane can help to achieve the same level of aged strength as the reference binder when needed.

[0316] Table 1.4 shows that a single base (31) or a combination of bases in different ratios (32 and 33) can be used to achieve equally good mechanical properties.

[0317]

[0318]

[0319]

[0320]

[0321] This means in general that we are able to produce a binder composition without phenol and formaldehyde, which contains a high content of lignin based on renewable materials, has comparable mechanical properties to the reference system and can be produced in a simpler and cheaper way.

[0322] Production Examples

[0323] Comparative Example 1:

[0324] This binder is a phenol-formaldehyde resin modified with urea, PUF-resol.

[0325] A phenol-formaldehyde resin was prepared by reacting a 37% aqueous formaldehyde solution (606 kg) and phenol (189 kg) in the presence of a 46% aqueous potassium hydroxide solution (25.5 kg) at a reaction temperature of 84°C with a heating rate to the reaction temperature of about 1°C / min. The reaction was continued at 84°C until the resin had an acid resistance of 4 and most of the phenol was converted. Then urea (241 kg) was added and the mixture was cooled.

[0326] Acid tolerance (AT) means the factor by which a given volume of a binder can be diluted with acid without the mixture becoming turbid (the binder precipitates). Sulfuric acid is used to determine the stop criteria in the production of a binder, and an acid tolerance lower than 4 indicates that the binder reaction is finished.

[0327] To measure AT, a titrant is prepared by diluting 2.5 ml of concentrated sulfuric acid (> 99%) with 1 L of ion exchange water. The 5 ml of binder to be studied is then titrated with this titrant at room temperature while the binder is kept in motion by hand shaking; if desired, a magnetic stirrer and a magnetic bar can be used. The titration is continued until a slight turbidity appears in the binder, which does not disappear when the binder is shaken.

[0328] The acid tolerance (AT) is calculated by dividing the amount of acid used for the titration (mL) by the amount of sample (mL):

[0329] AT = (titration volume used (mL)) / (sample volume (mL))

[0330] Using the resulting urea-modified phenol-formaldehyde resin, a binder is prepared by adding 25% ammonia water (90 L) and ammonium sulfate (13.2 kg), followed by water (1300 kg).

[0331] The binder solid content is then measured as described above, and the mixture is diluted with the required amount of water and silane (15% binder solid content solution, 0.5% silane of the binder solids) for mechanical measurements.

[0332] The binder obtained from this comparative example is used to produce 100 mm high density (145 kg / m 3 ) asbestos products. The curing oven temperature is set to 275 °C.

[0333] Comparative Example 2:

[0334] In a 6000 liter reactor, 3267 kg of water is added, followed by 287 kg of ammonia water (24.7%). Then, 1531 kg of lignin UPM BioPiva 100 is slowly added over a period of 30 to 45 minutes. The mixture is heated to 40 °C and kept at this temperature for 1 hour. After 1 hour, the undissolved lignin is checked. This can be done by checking the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in the brownish binder. The color of the lignin solution changes from brown to bright black during the dissolution step.

[0335] After the lignin is completely dissolved, 1 liter of antifoam (Antifoam 11-10 from is added. The batch temperature is kept at 40 °C. ​

[0336] Then the addition of 307.5 kg 35% hydrogen peroxide was started. The hydrogen peroxide was added at a rate of 200-300 liters / hour. The first half of the hydrogen peroxide was added at a rate of 200 liters / hour, after which the rate was increased to 300 liters / hour.

[0337] During the addition of hydrogen peroxide, the temperature of the reaction mixture was controlled by heating or cooling to reach a final reaction temperature of 65 °C.

[0338] The final product was analyzed for COOH group content, dry solids content, pH, viscosity and residual H202.

[0339] 1500 kg of this oxidized lignin (18.2% solids content) was mixed with 36 kg Primid XL552 (100% solids content) and 71 kg PEG 200 (100% solids content). Finally, 1.5 kg of silane (Momentive VS-142, 40% activity) was added and mixed. The binder prepared in this way was used to produce 100 millimeter high density (145 kg / m 3 ) mineral wool production trial.

[0340] The binder obtained from this comparative example was used to produce 100 mm high density (145 kg / m 3 ) asbestos product. The curing oven temperature was set to 275 °C.

[0341] Comparative Example 3:

[0342] Comparative Example 3 was like Comparative Example 1, but the curing oven temperature was set to 240 °C.

[0343] Comparative Example 4:

[0344] Comparative Example 4 was like Comparative Example 2, but the curing oven temperature was set to 240 °C.

[0345] Example 1:

[0346] Example 1 was used to produce an asbestos product at a curing oven temperature set to 275 °C.

[0347] 1182 liters of water and 96 liters of NH4OH (24.7%) were mixed, after which 512.0 kg of lignin (UPM Biopiva 100) was slowly added to it under high speed stirring for 30 minutes. Dissolution was facilitated by heating the mixture to 60 °C. A sample was taken for analysis of undissolved lignin using Hegman Scale and pH measurement. After dissolution, 208 kg of Primid XL552 solution (pre-prepared 31 wt% aqueous solution) and 90 kg of PEG 200 (100% solids content) were added and mixed.

[0348] The binder obtained from this example was used to produce 100 mm high density (145 kg / m 3 ) asbestos products. The curing oven temperature was set to 275°C.

[0349] Example 2 was performed as example 1, but the curing oven temperature was set to 240°C.

[0350] Testing of asbestos products:

[0351] The high density products have been performance checked according to the product standard DS / EN 13162:2012+A1 :2015 for factory made mineral wool (MW) products, i.e. relevant mechanical properties in addition to the other basic properties of the asbestos products have been checked.

[0352] The testing was performed on slabs, where the test samples were cut according to the size specifications and the number of test samples needed to obtain one test result as described in EN 13162 for each different test method. According to EN 13162, each stated value of mechanical property is an average of multiple results.

[0353] Compressive stress

[0354] The compressive stress at 10% deformation (σ10%) was determined according to DS / EN 826:2013 "Determination of compressive properties". After grinding the surface, at least 3 test samples of 300 x 300 mm of the full product thickness were measured (one result was obtained).

[0355] Delamination (tensile strength perpendicular to the plane)

[0356] The tensile strength perpendicular to the plane (σmt) was determined according to DS / EN 1607:2013. At least 3 test samples of 300 x 300 mm of the full product thickness were measured to obtain one result.

[0357] The tensile strength perpendicular to the plane of the test samples after exposure to accelerated ageing was further determined to evaluate the ageing durability, where two different methods were applied:

[0358] Ageing test (climate chamber and autoclave):

[0359] Method 1 (climate chamber):

[0360] The test samples were exposed to hygrothermal action in a climate chamber at (70 ± 2) °C and (95 ± 5) % relative humidity for 7, 14 and 28 days (Nordtest method NT Build 434:1995.05).

[0361] Method 2 (autoclave):

[0362] The test samples are exposed to hygrothermal action in a pressure boiler at (121 ± 2) °C and (95 ± 5) % relative humidity for 15 minutes.

[0363] For the test, 5 similar test samples of 300 x 300 mm of full product thickness are cut from the same slab and the tensile strength of one test sample without pre-treatment is measured.

[0364] The other test samples are exposed to accelerated ageing, wherein 3 test pieces are treated according to Method 1 : 1 for 7 days, 1 for 14 days and 1 for 28 days; 1 test piece is treated according to Method 2. After the final pre-treatment, the measurements are carried out and the ageing resistance is determined.

[0365] Water absorption

[0366] The short-term water absorption has been determined according to DS EN 1609:2013 Method A using 4 separate test samples of 200 x 200 mm of full product thickness to obtain one result.

[0367] The dimensional stability is determined according to DS / EN 1604:2013 "Determination of dimensional stability under specified conditions", but instead of the conditions specified in EN 1604 (48 hours, 70 °C, 90 % RH), the conditioned thickness, e.g. the determination of the thickness change (Δεp), is evaluated after 28 days at (70 ± 2) °C and (95 ± 5) % RH in a climate chamber.

[0368] The determination of the dimensions of the product and test samples is carried out according to the relevant test methods DS / EN 822:2013 "Determination of length and width" and DS / EN 823:2013 "Determination of thickness".

[0369] The determination of the binder content is carried out according to DS / EN 13820:2003 "Determination of organic content", wherein the binder content is defined as the amount of organic material that is burnt off at a given temperature, here (590 ± 20 °C) for at least 10 minutes or longer until the mass is constant. The determination of the loss on ignition includes at least 10 g of asbestos, which is uniformly distributed on the test sample using a punch (ensuring that the entire product thickness is included), corresponding to 8-20 incisions (minimum 8 incisions).

[0370] The binder content is taken as the LOI. The binder includes oil and other binder additives.

[0371] Table 2

[0372]

[0373]

[0374]

[0375]

[0376]

Claims

1. An aqueous binder composition for mineral fibres, having a pH of > 8, which is free of phenol and formaldehyde, comprising: - component (i) in the form of one or more sulphate lignins having a carboxylic acid group content of 0.03 to 0.9 mmol / g, based on the dry weight of the sulphate lignin; - component (ii) in the form of one or more crosslinkers in an amount of 1 to 50 wt%, based on the dry weight of component (i); - component (iii) in the form of one or more polyethylene glycol plasticizers in an amount of 0.5 to 60 wt%, based on the dry weight of component (i), wherein the component (ii) is in the form of one or more crosslinkers selected from the group consisting of: beta-hydroxyalkylamide crosslinkers and / or oxazoline crosslinkers, and / or polyfunctional organic amines, and / or epoxy compounds having a molecular weight of more than 500, or one or more flexible oligomers or polymers, and / or polyethyleneimines, polyvinyl amines, fatty amines; and / or fatty amides; and / or dimethoxy acetaldehyde, glycolic aldehyde, glyoxylic acid; and / or polyester polyols; and / or starches, modified starches, CMC; and / or polyfunctional carbodiimides; and / or melamine-based crosslinkers, with the proviso that the composition does not contain a crosslinking agent selected from epoxide compounds having a molecular weight M W of 500 or less.

2. The aqueous binder composition of claim 1, wherein component (i) has a carboxylic acid group content of 0.15 to 0.6 mmol / g, based on the dry weight of the sulphate lignin.

3. The aqueous binder composition of claim 1 or 2, wherein component (i) is in the form of one or more sulphate lignins having an average carboxylic acid group content of less than 1.8 groups per macromolecule, taking into account the number average molecular weight of component (i).

4. The aqueous binder composition of claim 1 or 2, wherein component (i) is in the form of one or more sulphate lignins having an average carboxylic acid group content of less than 1.4 groups per macromolecule, taking into account the number average molecular weight of component (i).

5. The aqueous binder composition of claim 1 or 2, wherein component (i) is in the form of one or more sulphate lignins having an average carboxylic acid group content of less than 1.1 groups per macromolecule, taking into account the number average molecular weight of component (i).

6. The aqueous binder composition of claim 1 or 2, wherein component (i) is in the form of one or more sulphate lignins having an average carboxylic acid group content of less than 0.7 groups per macromolecule, taking into account the number average molecular weight of component (i).

7. The aqueous binder composition of claim 1 or 2, wherein component (i) has a nitrogen content of < 1.2 wt%, based on the dry weight of component (i).

8. The aqueous binder composition of claim 1 or 2, wherein component (i) has a nitrogen content of < 0.5 wt%, based on the dry weight of component (i).

9. The aqueous binder composition of claim 1 or 2, wherein component (i) has a nitrogen content of < 0.3 wt%, based on the dry weight of component (i).

10. The aqueous binder composition of claim 1 or 2, wherein component (i) has a phenolic OH group content of 2.0 to 5.0 mmol / g, based on the dry weight of the sulfite lignin.

11. The aqueous binder composition of claim 1 or 2, wherein component (i) has a phenolic OH group content of 2.0 to 4.0 mmol / g, based on the dry weight of the sulfite lignin.

12. The aqueous binder composition of claim 1 or 2, wherein component (i) has a phenolic OH group content of 2.5 to 3.5 mmol / g, based on the dry weight of the sulfite lignin.

13. The aqueous binder composition of claim 1 or 2, wherein component (i) has an aliphatic OH group content of 0.7 to 3.0 mmol / g, based on the dry weight of the sulfite lignin.

14. The aqueous binder composition of claim 1 or 2, wherein component (i) has an aliphatic OH group content of 0.7 to 2.5 mmol / g, based on the dry weight of the sulfite lignin.

15. The aqueous binder composition of claim 1 or 2, wherein component (i) has an aliphatic OH group content of 1.0 to 2.0 mmol / g, based on the dry weight of the sulfite lignin.

16. The aqueous binder composition of claim 1, wherein the component (ii) is in the form of one or more crosslinking agents selected from the group consisting of: alkanolamines, diamines; and / or epoxidized oils based on fatty acid triglycerides; and / or low Tg acrylic based polymers, low Tg vinyl based polymers, low Tg polyethers containing reactive functional groups selected from the group consisting of carbodiimide groups, anhydride groups, oxazoline groups, amino groups and epoxy groups; and / or polycaprolactones; and / or aliphatic multifunctional carbodiimides; and / or hexa(methylmethoxy)melamine based crosslinking agents.

17. The aqueous binder composition of claim 1 or 2, wherein the component (ii) comprises one or more crosslinking agents selected from the group consisting of beta-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

18. The aqueous binder composition of claim 1 or 2, comprising component (ii) in an amount of 4 to 20 wt%, based on the dry weight of component (i).

19. The aqueous binder composition of claim 1 or 2, comprising component (ii) in an amount of 6 to 12 wt%, based on the dry weight of component (i).

20. The aqueous binder composition of claim 1 or 2, wherein component (iii) comprises one or more plasticizers having a boiling point of 100 to 380 °C.

21. The aqueous binder composition of claim 1 or 2, wherein component (iii) comprises one or more plasticizers having a boiling point of 120 to 300 °C.

22. The aqueous binder composition of claim 1 or 2, wherein component (iii) comprises one or more plasticizers having a boiling point of 140 to 250 °C.

23. The aqueous binder composition of claim 1 or 2, wherein component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol.

24. The aqueous binder composition of claim 1 or 2, wherein component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 4,000 g / mol.

25. The aqueous binder composition of claim 1 or 2, wherein component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 1,000 g / mol.

26. The aqueous binder composition of claim 1 or 2, wherein component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 500 g / mol.

27. The aqueous binder composition of claim 1 or 2, wherein component (iii) comprises one or more polyethylene glycols having an average molecular weight of 200 to 400 g / mol.

28. The aqueous binder composition of claim 1 or 2, wherein the component (iii) is present in an amount of 2.5 to 25 wt.%, based on the dry weight of component (i).

29. The aqueous binder composition of claim 1 or 2, wherein the component (iii) is present in an amount of 3 to 15 wt.%, based on the dry weight of component (i).

30. The aqueous binder composition of claim 1 or 2, comprising a further component (iv) in the form of one or more coupling agents.

31. The aqueous binder composition of claim 1 or 2, comprising a further component (iv) in the form of one or more organofunctional silanes.

32. The aqueous binder composition of claim 1 or 2, further comprising a component (v) in the form of one or more components selected from the group consisting of bases.

33. The aqueous binder composition of claim 1 or 2, further comprising a component (v) in the form of one or more components selected from the group consisting of ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, amines or any salts thereof.

34. The aqueous binder composition of claim 1 or 2, comprising a further component in the form of urea.

35. The aqueous binder composition of claim 1 or 2, comprising a further component in the form of urea in an amount of 5 to 40 wt.%, based on the dry weight of component (i).

36. The aqueous binder composition of claim 1 or 2, comprising a further component in the form of urea in an amount of 10 to 30 wt.%, based on the dry weight of component (i).

37. The aqueous binder composition of claim 1 or 2, comprising a further component in the form of urea in an amount of 15 to 25 wt.%, based on the dry weight of component (i).

38. The aqueous binder composition of claim 1 or 2, comprising a further component in the form of one or more silicone resins.

39. The aqueous binder composition of claim 1 or 2, wherein the aqueous binder composition does not contain ammonium-oxidized lignin.

40. A method of producing a bonded mineral fibre product, the method comprising the steps of: contacting mineral fibers with the binder composition of any one of claims 1-39; and curing the binder composition.

41. A mineral fiber product comprising mineral fibers in contact with a binder resulting from curing the binder composition of any one of claims 1-39.

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