Insulating product

Abstract

The present invention relates to a method for manufacturing an insulating product and a novel insulating product, wherein the insulating product is made by using an adhesive and curing the adhesive to adhere a facing to at least one main surface of a man-made vitreous fiber batt contained in a matrix containing an adhesive. The adhesive is an aqueous composition comprising: - component (i), which is in the form of one or more lignin oxides; - component (ii), which is in the form of one or more crosslinking agents; - component (iii), which is in the form of one or more plasticizers.

Description

Technical Field

[0001] The present invention relates to insulation products for use in sound insulation, heat insulation, fire protection and the like. In particular, the present invention relates to a method of manufacturing such insulation products and a system including such insulation products. Background Art

[0002] It is well known to provide insulation products for sound insulation, heat insulation and fire protection. A common form of such products is an insulation element in the form of a batt and having a facing adhered to the main surface of the batt.

[0003] Importantly, the adhesive for adhering the facing to the batt has suitable properties. In particular, it is important that the bond strength (usually defined as peel strength) is sufficient.

[0004] Phenolic resins are commonly used as adhesives for the facing. This is particularly useful for insulation elements formed from a matrix of man-made vitreous fibres (MMVF) bonded by a binder, since phenolic resins are commonly already used as binders for such products. Phenolic adhesives work well and are commonly used in commercial practice.

[0005] Phenolic resins can be produced economically and can be extended with urea before being used as adhesives. However, existing and proposed legislation aimed at reducing or eliminating formaldehyde emissions has led to the development of formaldehyde-free adhesives, such as adhesive compositions based on polycarboxyl polymers and polyols or polyamines, such as those disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, US-A-5,318,990 and US-A-2007 / 0173588.

[0006] Another group of non-phenolic adhesives are the addition / elimination reaction products of aliphatic and / or aromatic acid anhydrides and alkanolamines, for example, such as those disclosed in WO 99 / 36368, WO 01 / 05725, WO 01 / 96460, WO 02 / 06178, WO 2004 / 007615 and WO2006 / 061249. These adhesive compositions are water-soluble and exhibit excellent adhesion properties in terms of cure rate and cure density.

[0007] WO 2008 / 023032 discloses a urea-modified adhesive of this type, which provides mineral wool products with reduced hygroscopicity.

[0008] These substances can in principle be used as adhesives for finishing artificial vitreous fiber felts in a matrix containing an adhesive. However, since some of the starting materials used to produce these adhesives are rather expensive chemicals, there is currently a need to provide adhesives that can be produced economically and are formaldehyde-free.

[0009] A further effect associated with previously known aqueous adhesive compositions for mineral fiber products is that at least most of the starting materials used to produce these adhesives are derived from fossil fuels. Consumers are increasingly preferring products that are produced entirely or at least partly from renewable materials, and thus there is a need to provide adhesives for mineral fiber or mineral wool products that are at least partly produced from renewable materials.

[0010] Another effect associated with previously known aqueous adhesive compositions for mineral fiber products is that they include components that are corrosive and / or harmful. This requires protective measures to be taken on the machinery involved in the production of mineral wool products to prevent corrosion, and also requires safety measures to be taken for the personnel operating the machinery. This results in increased costs and health problems, and thus there is a need to provide adhesive compositions with a reduced content of corrosive and / or harmful substances.

[0011] Meanwhile, many adhesives for mineral fiber products have been provided that are largely based on renewable starting materials. In many cases, these adhesives that are largely based on renewable resources are also formaldehyde-free.

[0012] However, many of these adhesives are still relatively expensive because they are based on relatively expensive base materials, and thus it would be uneconomical to use them as adhesives for bonding finishes to insulation elements. Summary of the Invention

[0013] Accordingly, an object of the present invention is to provide an adhesive composition that is particularly suitable for bonding a finish to an artificial vitreous fiber felt in a matrix containing an adhesive, which uses renewable materials as starting materials, reduces or eliminates corrosive and / or harmful materials, and has a relatively low production cost.

[0014] A further object of the present invention is to provide an insulation product formed from an artificial vitreous fiber felt in a matrix containing an adhesive, the felt having a finish bonded thereto, wherein the bonding performance is good, particularly as good as those provided by phenolic adhesives, but which minimizes the disadvantages of phenolic adhesives.

[0015] According to a first aspect of the present invention, we provide a method of manufacturing an insulation product, the method comprising:

[0016] Provide a batt of man-made vitreous fibres (MMVF) in a matrix comprising a binder, wherein the batt of man-made vitreous fibres comprises at least one major surface;

[0017] Provide a facing;

[0018] Attach the facing to at least one major surface of the batt of man-made vitreous fibres by using an adhesive; and

[0019] Cure the adhesive, wherein the adhesive is an aqueous adhesive composition comprising:

[0020] - Component (i), which is in the form of one or more oxidised lignins;

[0021] - Component (ii), which is in the form of one or more cross-linking agents;

[0022] - Component (iii), which is in the form of one or more plasticisers.

[0023] In this aspect of the invention, we use the adhesive as defined above. The advantage of doing so is that it has commercially acceptable adhesion properties and is indeed as good as the properties of phenolic resins, but without the disadvantages associated with phenolic resins.

[0024] According to a second aspect of the invention, we provide a method of manufacturing an insulation product, the method comprising:

[0025] Provide a batt of man-made vitreous fibres (MMVF) comprising an uncured binder, wherein the batt of man-made vitreous fibres comprises at least one major surface;

[0026] Provide a facing;

[0027] Apply the facing to at least one major surface of the batt of man-made vitreous fibres; and

[0028] Cure the binder to attach the facing to the major surface, wherein the binder is an aqueous binder composition comprising:

[0029] - Component (i), which is in the form of one or more oxidised lignins;

[0030] - Component (ii), which is in the form of one or more cross-linking agents;

[0031] - Component (iii), which is in the form of one or more plasticisers.

[0032] In this aspect of the invention, we use the binder as described above. The advantage of doing so is that it has the properties of a binder and provides adhesion between the facing and the batt, which are commercially acceptable and are indeed as good as the properties of phenolic resin, yet without the disadvantages associated with phenolic resin.

[0033] The compression and delamination strength of the batt can be comparable to that of a batt bonded with phenolic resin and is thus superior to known formaldehyde-free binders. This has the advantages of reduced sagging, better processability, and improved adhesion. The water absorption and moisture resistance can also be similar to that of a batt bonded with phenolic resin; compared with a batt bonded with phenolic resin, there is no formaldehyde release, so there is no restriction for indoor use, and the indoor environment is improved.

[0034] According to a third aspect of the invention, we provide an insulating product obtained by the method of the first or second aspect of the invention.

[0035] According to a fourth aspect of the invention, we provide an insulating element which is a man-made vitreous fiber (MMVF) batt bonded with a binder, wherein the man-made vitreous fiber batt includes at least one main surface and includes a facing, and wherein the facing is fixed to at least one main surface of the insulating element by an adhesive, and wherein the adhesive before curing comprises:

[0036] - component (i), which is in the form of one or more lignin oxides;

[0037] - component (ii), which is in the form of one or more cross-linking agents;

[0038] - component (iii), which is in the form of one or more plasticizers.

[0039] A preferred method of manufacturing an insulating product includes fixing a facing to at least one main surface of the batt when the binder of the MMVF is uncured, and the step of curing the binder also cures the binder in the MMVF matrix.

[0040] The insulating product formed by the method according to the first and second aspects of the invention or the insulating product according to the third and fourth aspects of the invention can be bonded together to form a composite insulating product.

[0041] The insulating product can form an external facade, a ventilated facade, an indoor ceiling insulating product, an internal wall insulating product, a roof insulating product, a ventilation duct or a channel sound-absorbing product.

[0042] The insulating product can form an external facade insulating product. The external facade insulating product can be used for insulating a cavity wall. The external facade insulating product can be used for insulating a ventilated facade. The density of the insulating product can be 20 kg / m 3To 80 kg / m 3 Within the range, preferably between 30 kg / m 3 To 70 kg / m 3 The insulating product may have a loss on ignition within the range of 2% to 5% by weight, preferably within the range of 2.5% to 4% by weight. Preferably, the facing is a non-woven glass fabric with an areal weight between 30 g / m 2 To 150 g / m 2 , preferably 30 g / m 2 To 100 g / m 2 Of non-woven glass fabric.

[0043] The insulating product can be used as a silencer and splitter, and an absorption material in air-conditioning and ventilation systems. The density of the insulating product can be within the range of 30 g / m 2 To 150 g / m 2 The insulating product may have a loss on ignition within the range of 1.5% to 4% by weight, preferably within the range of 2% to 3% by weight. Preferably, the facing is a glass fiber filament fabric with an areal weight between 90 g / m 2 To 180 g / m 2 Between.

[0044] The insulating product can be used in thermal insulation, ventilation and air-conditioning systems. The density of the insulating product can be within the range of 30 kg / m 3 To 150 kg / m 3 The insulating product may have a loss on ignition within the range of 1.5% to 4% by weight, preferably within the range of 2% to 3% by weight. Preferably, the facing is a non-woven glass fabric with an areal weight between 30 g / m 2 To 150 g / m 2 Between, preferably 30 g / m 2 To 100 g / m 2 Between.

[0045] The insulating product or insulating element can form a thermal insulation system.

[0046] The thermal insulation system can be used for thermal insulation of the inner or outer walls of a building. The thermal insulation system can be used for thermal insulation of the external ceiling of a heated building. In both applications, the role of the insulating product is to reduce the heat loss transmitted from the inside of the building.

[0047] For a thermal insulation system used for thermal insulation of the external wall of a building, such as an external thermal insulation composite system (ETICS), the insulating product can be placed on the external wall in two layers, the layer facing the wall and the layer facing outwards, and the insulating products of the layer facing the wall and the layer facing outwards are bonded with an adhesive. This can be done on-site, but it is preferably pre-assembled in the factory and adhered to each other according to the method.

[0048] Such a heat insulation system may include heat insulation products adhesively bonded to the exterior of a building. A rendering is applied to the insulation product to protect it from weathering. A base rendering is typically applied, which is reinforced with a woven fabric layer and covered by a topcoat rendering. When using synthetic resin renderings, the combined thickness of the two renderings applied is from about 2 mm to about 7 mm, preferably less than 3 mm, while the thickness of a mineral rendering system can reach a range from about 8 mm to about 20 mm. The insulation products typically have to be fixed by insulation fasteners, i.e., connected to the exterior wall. Here, the part of the adhesive that bonds the insulation product to the support substrate, i.e., the exterior wall, is only used to assist installation, while the stiffness of the insulation product can withstand the increased shear stress caused by the shrinkage of the rendering.

[0049] The heat insulation system may include an insulation product or an insulation element, wherein the insulation product or the insulation element further includes an aerogel.

[0050] The heat insulation system may include at least two insulation products, each insulation product containing from 25 wt% to 95 wt% of aerogel, from 5 wt% to 75 wt% of inorganic fibers, and from 0 wt% to 70 wt% of inorganic fillers. The insulation products may be interconnected by an adhesive. Suitable aerogels are described in detail in WO 2012 / 098463.

[0051] The insulation product formed by the method according to the first and second aspects of the present invention or the insulation product according to the third and fourth aspects of the present invention can be used for heat insulation and / or sound insulation of a flat roof or a flat-sloped roof. The insulation product can form a roof system.

[0052] When the insulation product is used for roof applications, the insulation product can be a standard laminated or rolled base insulation product. The density of the insulation product can be in the range of 100 kg / m 3 to 200 kg / m 3 , preferably in the range of 140 kg / m 3 to 180 kg / m 3 . The loss on ignition of the insulation product can be in the range of 3 wt% to 8 wt%, preferably in the range of 3.5 wt% to 5 wt%. Preferably, the facing is a non-woven glass gauze with a mineral coating, and its areal weight is in the range of 150 g / m 2 to 350 g / m 2 .

[0053] When the insulation product is used for roof applications, the insulation product can be a sheet-like base insulation product. The density of the insulation product can be in the range of 80 kg / m 3 to 120 kg / m 3 . The loss on ignition of the insulation product can be in the range of 3 wt% to 8 wt%, preferably in the range of 3.5 wt% to 5 wt%. Preferably, the facing has an areal weight in the range of 150 g / m2 between 150 g / m 2 and 350 g / m of non-woven glass scrim with a mineral coating.

[0054] The roofing system may include at least one insulating product formed by the method according to the first and second aspects of the present invention or an insulating product according to the third and fourth aspects of the present invention, a sub-structure carrying the insulating product, and a film covering the main surface of the insulating product. The film is preferably a waterproof film.

[0055] The roofing system can be used for a so-called warm roof, where the main insulation layer is placed immediately below the roof covering (i.e., the waterproof film). The three main options for connecting single-ply roofing systems are mechanical fastening, adhesion / cold gluing, and ballasting, so that the insulation layer and the film can be connected by the same or different methods.

[0056] Preferably, the roofing system includes an insulating product that includes a non-woven glass scrim facing with a mineral coating, and more preferably the facing has an areal weight between 150 g / m 2 and 350 g / m 2

[0057] The roofing system can be used to insulate a flat roof structure, whereby the insulating product is spread out in two layers on the flat roof, i.e., a top layer and a bottom layer, and the insulating product of the top layer is adhesively bonded to the insulating product of the bottom layer.

[0058] The insulating product may include a structural composite material that provides excellent strength and stability and typically includes engineered wood products, as well as the thermal insulation element of the present invention.

[0059] The method of the present invention includes providing a man-made vitreous fiber batt containing an adhesive. This can be in the form of an insulating element. The man-made vitreous fiber batt can be made by casting a wet or fluid material (e.g., they can be made from wet-laid mineral fibers), but preferably forms an insulating element of air-laid mineral fibers, typically bonded in a matrix with an adhesive.

[0060] ​The binder can be any binder known for binding MMVF. The binder is preferably an organic binder, such as a phenolic binder, a urea formaldehyde binder, a phenol urea formaldehyde binder or a melamine formaldehyde binder. The conventionally used phenolic or phenol-urea-formaldehyde (PUF) type resol binder optionally contains a sugar component. For these binders without sugar components, reference is made, for example, to EP 0148050 and EP 0996653. For these binders with sugar components, see WO 2012 / 076462. It can be a formaldehyde-free binder, such as a binder composition based on polycarboxyl polymers and polyols or polyamines, such as those disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, US-A-5,318,990 and US-A-2007 / 0173588.

[0061] Another group of non-phenolic binders that can be used for the MMVF matrix are the addition / -elimination reaction products of aliphatic and / or aromatic acid anhydrides and alkanolamines, for example, as disclosed in WO 99 / 36368, WO 01 / 05725, WO 01 / 96460, WO 02 / 06178, WO2004 / 007615 and WO 2006 / 061249. These binder compositions are water-soluble and exhibit excellent binding properties in terms of curing speed and curing density. WO 2008 / 023032 discloses a urea-modified binder of this type, which provides mineral wool products with reduced hygroscopicity.

[0062] The binder preferably used for MMVF is an aqueous binder composition, which comprises:

[0063] - component (i), which is in the form of one or more lignin oxides;

[0064] - component (ii), which is in the form of one or more crosslinking agents;

[0065] - component (iii), which is in the form of one or more plasticizers.

[0066] The following describes other preferred features of the binder in the context of materials used as binders. All the same preferred features apply when such materials are used as binders for artificial vitreous fiber felts containing binders.

[0067] The density of the artificial vitreous fiber felt in the matrix containing the binder is preferably in the range of 6 kg / m 3 to 350 kg / m 3 and preferably in the range of 20 kg / m 3 to 200 kg / m 3 As described above, the preferred density depends on the intended use.

[0068] The loss on ignition (LOI) of the MMVF product is usually in the range of 0.5% to 8% by weight, preferably in the range of 2% to 5% by weight. The LOI is taken as the binder content and determined in a conventional manner according to European Standard EN 13820:2003. In addition to the main binding component, the binder usually also includes a small amount of oil and other organic binder additives.

[0069] In the matrix containing the binder, the mineral fibers in the man-made vitreous fiber batt usually have an average fiber diameter in the range of 3 to 8 microns.

[0070] The man-made vitreous fiber (MMVF) can have any suitable oxide composition. The fibers can be vitreous fibers, ceramic fibers, basalt fibers, slag fibers or rock or stone fibers. The fibers are preferably of the type commonly known as rock, stone or slag fibers, most preferably stone fibers.

[0071] Stone fibers usually contain the following oxides, expressed as a percentage by weight:

[0072] SiO2: 30 to 51

[0073] CaO: 8 to 30

[0074] MgO: 2 to 25

[0075] FeO (including Fe2O3): 2 to 15

[0076] Na2O + K2O: not exceeding 10

[0077] CaO + MgO: 10 to 30.

[0078] In a preferred embodiment, the MMVF includes elements in the following amounts, calculated as a percentage by weight of the oxides:

[0079] SiO2: at least 30, 32, 35 or 37; not exceeding 51, 48, 45 or 43

[0080] Al2O3: at least 12, 16 or 17; not exceeding 30, 27 or 25

[0081] CaO: at least 8 or 10; not exceeding 30, 25 or 20

[0082] MgO: at least 2 or 5; not exceeding 25, 20 or 15

[0083] FeO (including Fe2O3): at least 4 or 5; not exceeding 15, 12 or 10

[0084] FeO + MgO: at least 10, 12 or 15; not exceeding 30, 25 or 20

[0085] Na2O + K2O: 0 or at least 1; not exceeding 10

[0086] CaO + MgO: at least 10 or 15; not exceeding 30 or 25

[0087] TiO2: 0 or at least 1; not exceeding 6, 4 or 2

[0088] TiO2 + FeO: at least 4 or 6; not exceeding 18 or 12

[0089] B2O3: 0 or at least 1; not exceeding 5 or 3

[0090] P2O5: 0 or at least 1; not exceeding 8 or 5

[0091] Others: 0 or at least 1; not exceeding 8 or 5.

[0092] The MMVF prepared by the method of the present invention preferably has the following composition by weight percentage:

[0093] SiO2 35 to 50

[0094] Al2O3 12 to 30

[0095] TiO2 at most 2

[0096] Fe2O3 3 to 12

[0097] CaO 5 to 30

[0098] MgO at most 15

[0099] Na2O 0 to 15

[0100] K2O 0 to 15

[0101] P2O5 at most 3

[0102] MnO at most 3

[0103] B2O3 at most 3.

[0104] Another preferred composition of MMVF has the following weight percentages:

[0105] SiO2 39% to 55% preferably 39% to 52%

[0106] Al2O3 16% to 27% preferably 16 to 26%

[0107] CaO 6% to 20% preferably 8% to 18%

[0108] MgO 1% to 5%, preferably 1% to 4.9%

[0109] Na2O 0% to 15%, preferably 2% to 12%

[0110] K2O 0% to 15%, preferably 2% to 12%

[0111] R2O (Na2O + K2O) 10% to 14.7%, preferably 10% to 13.5%

[0112] P2O5 0% to 3%, preferably 0% to 2%

[0113] Fe2O3 (total iron) 3% to 15%, preferably 3.2% to 8%

[0114] B2O3 0% to 2%, preferably 0 to 1%

[0115] TiO2 0% to 2%, preferably 0.4% to 1%

[0116] Others 0% to 2.0%.

[0117] Glass fibers generally contain the following oxides, by weight percentage:

[0118] SiO2: 50 to 70

[0119] Al2O3: 10 to 30

[0120] CaO: not exceeding 27

[0121] MgO: not exceeding 12.

[0122] Glass fibers may also contain the following oxides, by weight percentage:

[0123] Na2O + K2O: 8 to 18, especially Na2O + K2O greater than CaO + MgO

[0124] B2O3: 3 to 12.

[0125] Some glass fiber compositions may contain Al2O3: less than 2%.

[0126] The artificial vitreous fiber batt in the matrix contains a binder which, once cured, has a first major surface and a second major surface that are substantially parallel (and extend in the XY direction). They are joined by minor surfaces that are generally perpendicular to the major surfaces (and thus extend in the Z direction).

[0127] The method of the present invention involves providing a mineral melt. The mineral melt is provided in a conventional manner by providing mineral materials and melting them in a furnace. The furnace can be any known type of furnace used for producing the mineral melt of MMVF, such as a shaft furnace, such as a cupola furnace, a pot furnace or a cyclone furnace.

[0128] Any suitable method can be employed to form MMVF from a mineral melt by fibrillating. The fibrillating can be carried out by a spinneret process, in which the melt is centrifugally extruded through orifices in the wall of a spinning cup (spinneret, also known as internal centrifugation). Alternatively, the fibrillating can be by centrifugal fibrillating, by spraying the melt onto the outer surface of a fibrillating rotor and stripping, or stripping from a cascade of multiple fibrillating rotors that rotate about a substantially horizontal axis (cascade spinneret).

[0129] The fibrillating of the fibers is generally facilitated by an air jet around each rotor, and the fibers are entrained by the air and conveyed to a collector. The binder is sprayed onto the fibers, preferably before collection. This general type of method is well known and is particularly applicable to rock, stone or slag fibers. WO 96 / 38391 describes in detail a preferred equipment method and mentions a large amount of literature on the fibrillating process, which can also be used for manufacturing fibers. Other suitable equipment and processes are described in WO02 / 32821 and WO2015 / 055758.

[0130] Thus, the melt is formed into a cloud of fibers entrained in air, and the fibers are collected as a web on a conveyor belt and removed from the fibrillating equipment. The fiber web is then consolidated, which may involve cross-laying and / or longitudinal compression and / or vertical compression and / or winding around a mandrel to produce a cylindrical article for pipe insulation. Other consolidation processes can also be carried out.

[0131] The binder composition is preferably applied to the fibers when the fibers are a cloud entrained in air. Alternatively, it can be applied after collection on the conveyor belt, but this is less preferred.

[0132] Before the step of curing the binder for MMVF, a facing is preferably applied to the first major surface. This means that the binder for the facing can also be cured in the same curing step as the binder. However, the facing can also be applied after the binder of the MMVF matrix is cured, and then the step of binder curing is carried out.

[0133] In one embodiment, the curing is carried out at a temperature of 100 °C to 300 °C, such as 170 °C to 270 °C, such as 180 °C to 250 °C, such as 190 °C to 230 °C.

[0134] In a preferred embodiment, the curing is carried out in a conventional curing furnace for mineral wool production, preferably operating at a temperature of 150 °C to 300 °C, such as 170 °C to 270 °C, such as 180 °C to 250 °C, such as 190 °C to 230 °C.

[0135] In one embodiment, curing is carried out for a time of 30 seconds to 20 minutes, such as 1 minute to 15 minutes, such as 2 minutes to 10 minutes.

[0136] In a typical embodiment, curing is carried out for a time of 30 seconds to 20 minutes at a temperature of 150 °C to 250 °C.

[0137] The so-called insulation products of MMVF are also called mineral wool products. When used for building insulation, according to the unified European standard EN 13162:2012+A1:2015 "Thermal insulation products for buildings - Factory-made mineral wool (MW) products", the respective requirements are further specified.

[0138] The thickness of the insulation product is the vertical distance between the main surfaces of the product. This thickness is usually in the range of 20 mm to 400 mm and varies according to the intended use, as described above.

[0139] The facing can independently be any material known to be used as a facing for insulation products.

[0140] The facing can be flexible or rigid. Preferably it is a flexible facing. It can be a woven or non-woven fiberglass gauze or fabric, scrim, roving, fiberglass filaments, glass filament fabric, spunbond polyester mesh, foil, gas-phase film, moisture barrier, roof lining foil, and home decor.

[0141] The facing can be a non-woven fiberglass gauze with a mineral coating. This type of facing can be used in cases where the gauze or fabric provides additional strength or elasticity to the insulation product.

[0142] The facing, such as a non-woven fiberglass gauze with a mineral coating, can have an area weight in the range of 150 g / m 2 to 350 g / m 2 and preferably in the range of 200 g / m 2 to 300 g / m 2 of the area weight.

[0143] The facing can be fiberglass filaments or glass filament fabric. This type of facing can be used in cases where the insulation product is used for sound absorption reasons, for example, in mufflers / splitters of air conditioning and ventilation systems. The fiberglass filaments and glass filament fabrics used for the above applications need to meet specific fiber corrosion and hygiene standards and are therefore more durable than non-woven fabrics.

[0144] For example, the area weight of the facing of fiberglass filaments or glass filament fabric can be in the range of 90 g / m 2 to 180 g / m 2Within a range, preferably within 100 g / m 2 to 160 g / m 2 range.

[0145] Methods of applying a facing to an MMVF web are known and can be used in the present invention in a conventional manner. When the facing is flexible, it is usually provided by a roller. It is then adhesively bonded to the MMVF web continuously in-line.

[0146] In this method, an adhesive is usually applied to the facing before the facing contacts the main surface of the vitreous synthetic fiber web. However, the adhesive can be applied directly to the main surface of the vitreous synthetic fiber web where the facing is to be adhesively bonded.

[0147] The applied weight is preferably in the range of 40 g / m 2 to 400 g / m 2 of a liquid adhesive, preferably 50 g / m 2 to 200 g / m 2 , more preferably 60 to 150 g / m 2 .

[0148] The adhesive is preferably applied by spraying. Another method of application is to pass the facing through a coating bath containing the adhesive.

[0149] Insulating articles manufactured by the method according to the invention and insulating articles manufactured according to the fourth aspect of the invention can be used in any known insulating article application.

[0150] For example, it can be an external facade, a ventilated facade, an interior ceiling insulating article, an interior wall insulating article, a roof insulating article, a sound-absorbing article for a ventilation duct or passage, or form part of an external facade, a ventilated facade, an interior ceiling insulating article, an interior wall insulating article, a roof insulating article, a sound-absorbing article for a ventilation duct or passage.

[0151] The adhesive used according to the invention is in the form of an aqueous composition. Preferred features are discussed below. The MMVF web adhesively bonded with the adhesive can also be of the type discussed below, and all the same preferred features apply.

[0152] The aqueous adhesive and / or binder comprises:

[0153] - component (i), which is in the form of one or more oxidized lignins;

[0154] - component (ii), which is in the form of one or more crosslinking agents;

[0155] - component (iii), which is in the form of one or more plasticizers.

[0156] In a preferred embodiment, the binder and / or adhesive used according to the invention is free of formaldehyde.

[0157] For the purposes of this application, the term "formaldehyde-free" is defined as a mineral wool product in which the formaldehyde emission is less than 5 μg / m 2 / h, preferably less than 3 μg / m 2 / h. Preferably, the test for aldehyde release is carried out in accordance with ISO 16000.

[0158] Component (i)

[0159] Component (i) is in the form of one or more oxidized lignins.

[0160] Lignin, cellulose, and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be considered the glue that holds cellulose fibers together. Lignin contains hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, after cellulose, and is estimated to account for up to 20% to 30% of the total carbon contained in biomass, with a global total of over 1 billion tons of carbon.

[0161] Figure 1 Shows a portion of a possible lignin structure.

[0162] There are at least four groups of industrial lignins available on the market. These four groups are shown in Figure 3 . A possible fifth group, namely biorefinery lignin, is somewhat different as it is not described according to the extraction process but according to the process source, such as biorefinery, and thus it may be similar to or different from any of the other groups above. Each group is different from one another and is suitable for different applications. Lignin is a complex, heterogeneous material that, depending on the source, consists of up to three different phenylpropane monomers. Softwood lignin is mainly made up of coniferyl alcohol units, see Figure 2 , and thus they are more homogeneous than hardwood lignins, which have a higher syringyl alcohol content, see Figure 2 . The appearance and consistency of lignin are quite variable and depend to a large extent on the process.

[0163] Figure 4 Shows a summary of the characteristics of these industrial lignins.

[0164] Lignosulfonates from the sulfite pulping process remain the largest commercially available lignin source, with a production capacity of 1.4 million tons. But aside from these, the kraft process is the most used pulping process currently and is gradually replacing the sulfite process. It is estimated that 78 million tons of lignin are produced annually from kraft pulp globally, but most of it is burned for steam and energy. The current kraft recovery capacity is estimated at 160,000 tons, but there are reports that the current recovery is only about 75,000 tons. Kraft lignin is developed from black liquor, which is the waste liquor of the kraft or sulfate process. Currently, there are 3 well-known processes used to produce kraft lignin: LignoBoost, LignoForce, and SLRP. The similarity of these 3 processes is that they all involve adding CO2 to lower the pH to 9 to 10, followed by acidification to further lower the pH to about 2. The final step involves some combination of washing, leaching, and filtration to remove ash and other contaminants. These three processes are at different commercialization stages globally.

[0165] The kraft process introduces mercaptan groups and stilbenes while retaining some carbohydrates. Sodium sulfate also exists as an impurity due to the precipitation of lignin from the liquor with sulfuric acid, but this problem can potentially be avoided by changing the way lignin is separated. The kraft process results in a large number of phenolic hydroxyl groups, and when these groups are ionized (above pH ~10), this lignin is water-soluble.

[0166] The purity of commercial kraft lignin is generally higher than that of lignosulfonates. The molecular weight is from 1000 g / mol.s to 3000 g / mol.s.

[0167] Alkali lignin is derived from the sodium hydroxide pulping process and is mainly used for wheat straw, bagasse, and flax. The properties of alkali lignin are similar to those of kraft lignin in terms of solubility and T g This process does not use sulfur and has no covalently bound sulfur. The ash level is very low. Alkali lignin has low solubility in neutral and acidic media but is completely soluble at pH 12 and higher.

[0168] The lignosulfonate process introduces a large number of sulfonate groups, making lignin soluble in water and also in acidic aqueous solutions. The sulfur content of lignosulfonates is as high as 8% as sulfonates, while kraft lignin contains 1% to 2% sulfur, mainly bound to the lignin. The molecular weight of lignosulfonates is from 15,000 g / mol to 50,000 g / mol. Compared with other types of lignin, this lignin contains more remaining carbohydrates and has a higher average molecular weight. The typical hydrophobic core of lignin and the large number of ionized sulfonate groups make this lignin attractive as a surfactant, and it is often applied in dispersing cement, etc.

[0169] Another type of lignin that is available is lignin produced in a biorefinery process, where carbohydrates are separated from lignin by a chemical or biochemical process, resulting in a carbohydrate-rich fraction. This remaining lignin is referred to as biorefinery lignin. The focus of a biorefinery is to produce energy and produce alternatives to products obtained from fossil fuels and petrochemicals as well as lignin. The lignin produced in this process is generally considered a low-value product or even a waste product and is mainly used for thermal combustion or as a low-grade feed or otherwise disposed of.

[0170] The availability of organosolv lignin is still considered at the pilot scale. The process involves using water and various organic solvents (most commonly ethanol) as well as some organic acids to extract lignin. The advantage of this process is that the lignin obtained has a higher purity, but compared to other industrial lignins, the cost is much higher, and the lignin obtained is dissolved in an organic solvent rather than water.

[0171] Previous attempts to use lignin as a basic compound for binders and / or binder compositions for mineral fibers have failed because it has proven difficult to find a suitable crosslinking agent to achieve the desired mechanical properties of the cured mineral wool products while avoiding harmful and / or corrosive components. Currently, lignin is used to replace petroleum-derived chemicals such as phenols in binders and / or binder applications or phenolic resins in asphalt. It is also used as a cement and concrete additive and in some aspects as a dispersant.

[0172] Crosslinking of polymers generally should provide improved properties such as mechanical, chemical, and heat resistance, etc. Lignin is particularly rich in phenolic and aliphatic hydroxyl groups, which can react to result in a crosslinked structure of lignin. Different lignins will also have other available functional groups. Depending on the specific source, the presence of these other groups depends to a large extent on the way lignin is separated from cellulose and hemicellulose (thiols in kraft lignin, sulfonates in lignosulfonates, etc.).

[0173] It has been found that by using oxidized lignin, binders and / or binder compositions can be prepared, enabling the manufactured mineral fiber products to have excellent properties.

[0174] In one embodiment, component (i) is in the form of one or more oxidized kraft lignins.

[0175] In one embodiment, component (i) is in the form of one or more oxidized soda lignins.

[0176] In one embodiment, component (i) is in the form of one or more ammonia-oxidized lignins. For the purposes of the present invention, the term "ammonia-oxidized lignin" should be understood as lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0177] In an alternative embodiment, the ammonia is partially or fully replaced by an alkali metal hydroxide, particularly sodium hydroxide and / or potassium hydroxide.

[0178] A typical oxidizing agent for preparing oxidized lignin is hydrogen peroxide.

[0179] In one embodiment, the ammonia-oxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides, or any salts thereof.

[0180] In one embodiment, based on the dry weight of component (i), the carboxylic acid group content of component (i) is from 0.05 mmol / g to 10 mmol / g, such as from 0.1 mmol / g to 5 mmol / g, such as from 0.20 mmol / g to 1.5 mmol / g, such as from 0.40 mmol / g to 1.2 mmol / g, such as from 0.45 mmol / g to 1.0 mmol / g.

[0181] In one embodiment, component (i) has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups.

[0182] It is believed that the carboxylic acid group content of the oxidized lignin plays an important role in the unexpected advantages for mineral fibers in the aqueous adhesives and / or binder compositions of the present invention. In particular, it is believed that the carboxylic acid groups of the oxidized lignin improve the crosslinking properties, thus conferring better mechanical properties to the cured mineral fiber products.

[0183] Component (ii)

[0184] Component (ii) is in the form of one or more crosslinking agents.

[0185] In one embodiment, component (ii) in one embodiment comprises one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

[0186] β-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 β-hydroxyalkylamide crosslinking agents cure through esterification reactions to form multiple ester bonds. The hydroxyl functionality of the β-hydroxyalkylamide crosslinking agent should be at least 2 on average, preferably greater than 2, more preferably 2 to 4, in order to obtain an optimal curing response.

[0187] A crosslinking agent containing an oxazoline group is a polymer containing more than one oxazoline group per molecule, and generally, a crosslinking agent containing oxazoline can be easily obtained by polymerizing an oxazoline derivative. Patent US6818699 B2 discloses such a process.

[0188] In one embodiment, component (ii) is an epoxy oil based on fatty acid triglyceride.

[0189] It should be noted that epoxy oils based on fatty acid triglycerides are not considered dangerous, and thus the use of these compounds in the adhesives and / or adhesive compositions of the present invention does not render the handling of these compositions unsafe.

[0190] In one embodiment, component (ii) is a molecule having 3 or more epoxy groups.

[0191] In one embodiment, component (ii) is one or more flexible oligomers or polymers, such as low Tg acrylic polymers, such as low Tg vinyl polymers, such as low Tg polyethers, which contain reactive functional groups, such as carbodiimide groups, such as acid anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0192] In one embodiment, component (ii) is selected from crosslinking agents participating in the curing reaction, such as hydroxyalkylamides, alkanolamines, reaction products of alkanolamines and polycarboxylic acids. The reaction products of alkanolamines and polycarboxylic acids can be found in US6706853B1.

[0193] Without wishing to be bound by any particular theory, it is believed that the very advantageous properties of the aqueous adhesives and adhesive compositions according to the present invention are due to the interaction of the oxidized lignin used as component (i) with the above crosslinking agents. It is believed that the presence of carboxylic acid groups in the oxidized lignin enables the oxidized lignin to crosslink very effectively.

[0194] In one embodiment, component (ii) is one or more crosslinking agents selected from polyfunctional organic amines such as alkanolamines, diamines such as hexamethylenediamine, triamines.

[0195] In one embodiment, component (ii) is one or more crosslinking agents selected from polyethyleneimine, polyvinylamine, fatty amines.

[0196] In one embodiment, component (ii) is one or more fatty amides.

[0197] In one embodiment, component (ii) is one or more crosslinking agents selected from dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid.

[0198] In one embodiment, component (ii) is one or more crosslinking agents selected from polyester polyols such as polycaprolactone.

[0199] In one embodiment, component (ii) is one or more crosslinking agents selected from starch, modified starch, CMC.

[0200] In one embodiment, component (ii) is one or more crosslinking agents in the form of aliphatic polyfunctional carbodiimide.

[0201] In one embodiment, component (ii) is one or more crosslinking agents selected from melamine-based crosslinking agents such as hexakis(methoxymethyl)melamine (HMMM) crosslinking agents.

[0202] 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.).

[0203] Component (ii) can also be any mixture of the above compounds.

[0204] In one embodiment, based on the dry weight of component (i), the adhesive and / or binder composition according to the invention comprises component (ii) in an amount of 1 wt% to 40 wt%, such as 4 wt% to 20 wt%, such as 6 wt% to 12 wt%

[0205] Component (iii)

[0206] Component (iii) is in the form of one or more plasticizers.

[0207] In one embodiment, component (iii) is in the form of one or more plasticizers selected from: polyols such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ether, polyethers, phthalates and / or acids 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 polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides (such as urea / urea) or any mixture thereof.

[0208] In one embodiment, component (iii) is in the form of one or more plasticizers selected from: carbonates such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds having a structure similar to lignin such as vanillin, acetosyringone, solvents used as coalescing agents such as alcohol ethers, and polyvinyl alcohol.

[0209] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from: polyethylene glycol, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or other esters, solvents used as coalescing agents such as alcohol ethers, acrylic polymers, and polyvinyl alcohol.

[0210] In one embodiment, component (iii) is one or more reactive plasticizers selected from: carbonates such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, dicarboxylic or tricarboxylic acids such as adipic acid, or lactic acid, and / or vanillic acid and / or ferulic acid, polyurethane dispersions, acrylic polymers having free carboxyl groups, compounds having a structure similar to lignin such as vanillin, acetosyringone.

[0211] In one embodiment, component (iii) is in the form of one or more plasticizers selected from fatty alcohols, monohydric alcohols such as pentanol, stearyl alcohol.

[0212] In one embodiment, component (iii) comprises one or more plasticizers selected from polyethylene glycol, polyethylene glycol ethers.

[0213] Another particularly unexpected aspect of the present invention is that the use of plasticizers having a boiling point above 100 °C, especially from 140 °C to 250 °C, significantly improves the mechanical properties of the mineral fiber products according to the present invention, although in view of their boiling points, these plasticizers are likely to at least partially evaporate during the curing of the aqueous binder and / or adhesive in contact with the mineral fibers.

[0214] In one embodiment, component (iii) comprises one or more plasticizers having a boiling point above 100 °C, such as from 110 °C to 280 °C, more preferably from 120 °C to 260 °C, more preferably from 140 °C to 250 °C.

[0215] It is believed that the effectiveness of these plasticizers in the aqueous binder and / or adhesive composition according to the present invention is related to their role in increasing the mobility of oxidized lignin during the curing process. It is believed that the increased mobility of lignin or oxidized lignin during the curing process contributes to effective crosslinking.

[0216] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of from 150 g / mol to 50,000 g / mol, particularly from 150 g / mol to 4000 g / mol, more particularly from 150 g / mol to 1000 g / mol, preferably from 150 g / mol to 500 g / mol, and more preferably from 200 g / mol to 400 g / mol.

[0217] In one embodiment, component (iii) includes one or more polyethylene glycols having an average molecular weight of from 4000 g / mol to 25,000 g / mol, particularly from 4000 g / mol to 15,000 g / mol, and more particularly from 8000 g / mol to 12,000 g / mol.

[0218] In one embodiment, component (iii) is capable of forming covalent bonds with component (i) and / or component (ii) during the curing process. Such a component does not evaporate and remains as part of the composition, but is effectively modified so as not to introduce undesirable side effects such as water absorption in the cured article. Non-limiting examples of such components are caprolactone and acrylic polymers having free carboxyl groups.

[0219] In one embodiment, component (iii) is selected from fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.

[0220] In one embodiment, component (iii) is selected from one or more plasticizers selected from alkoxylates such as ethoxylates, such as butanol ethoxylate, such as butoxytriglycol.

[0221] In one embodiment, component (iii) is selected from one or more propylene glycols.

[0222] In one embodiment, component (iii) is selected from one or more ethylene glycol esters.

[0223] In one embodiment, component (iii) is selected from one or more plasticizers selected from: adipates, acetates, benzoates, cyclohexanecarboxylates, citrates, stearates, sorbates, caprates, azelates, butyrates, valerates.

[0224] In one embodiment, component (iii) is selected from one or more plasticizers selected from: phenol derivatives such as alkyl- or aryl-substituted phenols.

[0225] In one embodiment, component (iii) is selected from one or more plasticizers selected from: silanols, siloxanes.

[0226] In one embodiment, component (iii) is selected from one or more plasticizers selected from: sulfates such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates such as alkyl sulfonates, phosphates such as tripolyphosphates, such as tributyl phosphate.

[0227] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0228] In one embodiment, component (iii) is selected from one or more plasticizers selected from: monomeric amides such as acetamide, benzamide, fatty acid amides such as tall oil amide.

[0229] In one embodiment, component (iii) is selected from one or more plasticizers selected from: quaternary ammonium compounds such as betaine, distearyldimethylammonium chloride.

[0230] In one embodiment, component (iii) is selected from one or more plasticizers selected from: vegetable oils such as castor oil, palm oil, linseed oil, tall oil, soybean oil.

[0231] In one embodiment, component (iii) is selected from one or more plasticizers selected from: hydrogenated oils, acetylated oils.

[0232] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0233] In one embodiment, component (iii) is selected from one or more plasticizers selected from: alkyl polyglycosides, glucamides, aminoglucamides, sucrose esters, sorbitan esters.

[0234] It has unexpectedly been found that the addition of a plasticizer to the aqueous adhesive and / or binder composition according to the invention significantly improves the mechanical properties of the mineral fiber products according to the invention.

[0235] The term plasticizer refers to a substance that is added to a material to make the material softer, more flexible (by lowering the glass transition temperature Tg) and easier to process.

[0236] Component (iii) can also be any mixture of the above compounds.

[0237] In one embodiment, based on the dry weight of component (i), the content of component (iii) is from 0.5 wt% to 50 wt%, preferably from 2.5 wt% to 25 wt%, more preferably from 3 wt% to 15 wt%.

[0238] The aqueous adhesive and / or binder composition for mineral fibers comprises component (i) and (iia).

[0239] In one embodiment of the present invention, the aqueous binder and / or sizing composition for mineral fibers comprises:

[0240] - Component (i), which is in the form of one or more oxidized lignins;

[0241] - Component (iia), which is in the form of one or more modifiers.

[0242] The inventors have found that excellent sizing properties can also be achieved by a two-component system comprising component (i) in the form of one or more oxidized lignins and component (iia) in the form of one or more modifiers, and optionally any other components mentioned above and below.

[0243] In one embodiment, component (iia) is a modifier which is in the form of one or more compounds selected from epoxy oils based on fatty acid triglycerides.

[0244] In one embodiment, component (iia) is a modifier which is in the form of one or more compounds selected from molecules having 3 or more epoxy groups.

[0245] In one embodiment, component (iia) is a modifier which is in the form of one or more flexible oligomers or polymers, such as low Tg acrylic polymers, such as low Tg vinyl polymers, such as low Tg polyethers, which contain reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0246] In one embodiment, component (iia) is one or more modifiers selected from polyethyleneimine, polyvinylamine, and fatty amines.

[0247] In one embodiment, component (iia) is one or more modifiers selected from aliphatic polyfunctional carbodiimides.

[0248] Component (iia) can also be any mixture of the above compounds.

[0249] Without wishing to be bound by any particular theory, it is believed that the excellent sizing properties achieved by the binder and / or sizing composition for mineral fibers comprising components (i) and (iia) and optionally other components are due, at least in part, to the fact that the modifier used as component (iia) serves, at least in part, the functions of a plasticizer and a crosslinking agent.

[0250] In one embodiment, based on the dry weight of component (i), the aqueous adhesive and / or binder composition comprises component (iia) in an amount of 1 wt% to 40 wt%, such as 4 wt% to 20 wt%, such as 6 wt% to 12 wt%.

[0251] Other components

[0252] In some embodiments, the aqueous adhesive and / or binder composition used in the present invention comprises other components.

[0253] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention comprises a catalyst selected from inorganic acids, such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid, and / or phosphoric acid, and / or any of their salts, 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. The presence of such a catalyst can improve the curing performance of the aqueous adhesive and / or binder composition according to the present invention.

[0254] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention comprises a catalyst selected from Lewis acids, which can accept an electron pair from a donor compound to form a Lewis adduct, such as ZnCl2, Mg(ClO4)2, Sn[N(SO2-n-C8F17)2]4.

[0255] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention comprises a catalyst selected from metal chlorides, such as KCl, MgCl2, ZnCl2, FeCl3, and SnCl2.

[0256] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention comprises a catalyst selected from organometallic compounds, such as titanate catalysts and tin catalysts.

[0257] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, and copper ions.

[0258] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention further comprises other component (iv), which is in the form of one or more silanes.

[0259] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention comprises other component (iv), which is in the form of one or more coupling agents, such as organofunctional silanes.

[0260] 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.

[0261] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention further comprises component (v), which is in the form of one or more components selected from ammonia, amines or any salts thereof.

[0262] It has been found that when using oxidized lignin in component (i), the addition of ammonia, amines or any salts thereof as other components is particularly useful, wherein the oxidized lignin is not oxidized in the presence of ammonia.

[0263] In one embodiment, based on the dry weight of component (i), the aqueous binder and / or adhesive composition used in the present invention further comprises other components in the form of urea, especially in an amount of 5 wt% to 40 wt%, such as 10 wt% to 30 wt%, 15 wt% to 25 wt%.

[0264] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention further comprises one or more other components in the form of carbohydrates selected from sucrose, reducing sugars, especially glucose, polycarbohydrates and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, more preferably glucose syrup with a dextrose equivalent value of DE = 30 to less than 100, such as DE = 60 to less than 100, such as DE = 60 - 99, such as DE = 85 - 99, such as DE = 95 - 99.

[0265] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention further comprises other components in the form of one or more carbohydrates selected from sucrose and reducing sugars, and based on the dry weight of component (i), the amount is 5 wt% to 50 wt%, such as 5 wt% to less than 50 wt%, such as 10 wt% to 40 wt%, such as 15 wt% to 30 wt%.

[0266] In the context of the present invention, a binder or adhesive composition having a sugar content of 50 wt% or more based on the total dry weight of the binder or adhesive component is considered a sugar-based binder or adhesive. In the context of the present invention, a binder or adhesive composition having a sugar content of less than 50 wt% based on the total dry weight of the binder or adhesive component is considered a non-sugar-based binder or adhesive.

[0267] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention further comprises one or more other components in the form of surfactants, which are in the form of non-ionic and / or ionic emulsifiers, such as polyoxyethylene (4) lauryl ether, such as soy lecithin, such as sodium dodecyl sulfate.

[0268] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention comprises:

[0269] - Component (i), which is in the form of one or more lignin ammonia oxides, and based on the dry weight of component (i), its carboxylic acid group content is 0.05 mmol / g to 10 mmol / g, such as 0.1 mmol / g to 5 mmol / g, such as 0.20 mmol / g to 1.5 mmol / g, such as 0.40 mmol / g to 1.2 mmol / g, such as 0.45 mmol / g to 1.0 mmol / g;

[0270] - Component (ii), which is in the form of one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents, and / or it is in the form of one or more crosslinking agents selected from polyfunctional organic amines such as alkanolamines, diamines such as hexamethylenediamine, and triamines;

[0271] - Component (iii), which is in the form of one or more polyethylene glycols with an average molecular weight of 150 g / mol to 50000 g / mol, particularly 150 g / mol to 4000 g / mol, more specifically 150 g / mol to 1000 g / mol, preferably 150 g / mol to 500 g / mol, more preferably 150 g / mol to 300 g / mol, or it is in the form of one or more polyethylene glycols with an average molecular weight of 4000 g / mol to 25000 g / mol, particularly 4000 g / mol to 15000 g / mol, more specifically 8000 g / mol to 12000 g / mol; wherein based on the dry weight of component (i), preferably the amount of component (ii) contained in the aqueous binder and / or adhesive composition is 1 wt% to 40 wt%, such as 4 wt% to 20 wt%, 6 wt% to 12 wt%, and based on the dry weight of component (i), the content of component (iii) is 0.5 wt% to 50 wt%, preferably 2.5 wt% to 25 wt%, more preferably 3 wt% to 15 wt%.

[0272] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention comprises:

[0273] - Component (i), which is in the form of one or more ammonia-oxidized lignins, and based on the dry weight of component (i), its carboxylic acid group content is from 0.05 mmol / g to 10 mmol / g, such as from 0.1 mmol / g to 5 mmol / g, such as from 0.20 mmol / g to 1.5 mmol / g, such as from 0.40 mmol / g to 1.2 mmol / g, such as from 0.45 mmol / g to 1.0 mmol / g;

[0274] - Component (iia), which is in the form of one or more modifiers selected from epoxy oils based on fatty acid triglycerides.

[0275] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention comprises:

[0276] - Component (i), which is in the form of one or more ammonia-oxidized lignins, and the average carboxylic acid group content of each macromolecule of component (i) exceeds 1.5 groups, such as more than 2 groups, such as more than 2.5 groups;

[0277] - Component (ii), which is in the form of one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents, and / or which is in the form of one or more crosslinking agents selected from polyfunctional organic amines such as alkanolamines, diamines such as hexamethylenediamine, and triamines;

[0278] - Component (iii), which is in the form of one or more polyethylene glycols with an average molecular weight of 150 g / mol to 50,000 g / mol, particularly 150 g / mol to 4000 g / mol, more specifically 150 g / mol to 1000 g / mol, preferably 150 g / mol to 500 g / mol, more preferably 150 g / mol to 300 g / mol, or which is in the form of one or more polyethylene glycols with an average molecular weight of 4000 g / mol to 25,000 g / mol, particularly 4000 g / mol to 15,000 g / mol, more specifically 8000 g / mol to 12,000 g / mol; wherein based on the dry weight of component (i), preferably the aqueous binder and / or adhesive composition contains component (ii) in an amount of 1 wt% to 40 wt%, such as 4 wt% to 20 wt%, 6 wt% to 12 wt%, and based on the dry weight of component (i), the content of component (iii) is 0.5 wt% to 50 wt%, preferably 2.5 wt% to 25 wt%, more preferably 3 wt% to 15 wt%.

[0279] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention comprises:

[0280] - Component (i), which is in the form of one or more kinds of ammonia-oxidized lignin, and the average carboxylic acid group content of each macromolecule of component (i) exceeds 1.5 groups, such as more than 2 groups, such as more than 2.5 groups;

[0281] - Component (iia), which is in the form of one or more kinds of modifiers selected from epoxy oils based on fatty acid triglycerides.

[0282] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention consists essentially of the following:

[0283] - Component (i), which is in the form of one or more kinds of oxidized lignin;

[0284] - Component (ii), which is in the form of one or more kinds of cross-linking agents;

[0285] - Component (iii), which is in the form of one or more kinds of plasticizers.

[0286] - Component (iv), which is in the form of one or more kinds of coupling agents, such as organofunctional silanes;

[0287] - Optional component, which is in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0288] - Optional component, which is in the form of urea;

[0289] - Optional component, which is in the form of more reactive or non-reactive polysiloxanes;

[0290] - Optional hydrocarbon oil;

[0291] - Optional one or more surfactants;

[0292] - Water.

[0293] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention consists essentially of the following:

[0294] - Component (i), which is in the form of one or more kinds of oxidized lignin;

[0295] - Component (iia), which is in the form of one or more kinds of modifiers selected from epoxy oils based on fatty acid triglycerides.

[0296] - Component (iv), which is in the form of one or more kinds of coupling agents, such as organofunctional silanes;

[0297] - Optional component, which is in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0298] - An optional component, which is in the form of urea;

[0299] - An optional component, which is in the form of a more reactive or non-reactive polysiloxane;

[0300] - An optional hydrocarbon oil;

[0301] - An optional surfactant or surfactants;

[0302] - Water.

[0303] Oxidized lignin, which can be used as a component of the aqueous binder and / or adhesive composition for mineral fibers according to the present invention, and a method for preparing such oxidized lignin

[0304] Hereinafter, we describe the oxidized lignin that can be used as a component of the binder and / or adhesive composition and its preparation.

[0305] Method I for preparing oxidized lignin

[0306] The oxidized lignin that can be used as a component for the binder and / or adhesive of the present invention can be prepared by a method comprising contacting:

[0307] - Component (a), which comprises one or more lignins;

[0308] - Component (b), which comprises ammonia, one or more amine components, and / or any salt thereof;

[0309] - Component (c), which comprises one or more oxidants.

[0310] Component (a)

[0311] Component (a) comprises one or more lignins.

[0312] In one embodiment of the method, component (a) comprises one or more kraft lignins, one or more alkali lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins obtained from a biorefining process of lignocellulosic raw materials, or any mixture thereof.

[0313] In one embodiment, component (a) comprises one or more kraft lignins.

[0314] Component (b)

[0315] In one embodiment according to the present invention, component (b) comprises ammonia, one or more amino components, and / or any salts thereof. Without wishing to be bound by any particular theory, it is believed that replacing the alkali hydroxides used in previously known lignin oxidation processes with ammonia, one or more amino components, and / or any salts thereof plays an important role in improving the properties of the oxidized lignin prepared by the method according to the present invention.

[0316] Unexpectedly, it has been found that lignin oxidized in the presence of ammonia or an amine contains a large amount of nitrogen as part of the oxidized lignin structure. Without wishing to be bound by any particular theory, it is believed that when the oxidized lignin (prepared according to the present invention) is used in articles incorporating them into binder and / or adhesive compositions, the improved fire resistance of the oxidized lignin is at least partly due to the nitrogen content of the oxidized lignin structure.

[0317] In one embodiment, component (b) comprises ammonia and / or any salts thereof.

[0318] Without wishing to be bound by any particular theory, it is believed that the improved stability of the derivatized lignin prepared according to the present invention is at least partly due to the fact that ammonia is a volatile compound and thus evaporates from the final product or can be easily removed and reused. In contrast, it has proven difficult to remove residual amounts of the alkali hydroxides used in previously known oxidation processes.

[0319] However, in the present invention, it would be advantageous for component (b) to further comprise a relatively small amount of an alkali and / or alkaline earth metal hydroxide, such as sodium hydroxide and / or potassium hydroxide, in addition to ammonia, one or more amino components, and / or any salts thereof.

[0320] In some embodiments, where component (b) comprises an alkali and / or alkaline earth metal hydroxide, such as sodium hydroxide and / or potassium hydroxide, as a component in addition to ammonia, one or more amino components, and / or any salts thereof, the amount of the alkali and / or alkaline earth metal hydroxide is typically small, based on ammonia, such as 5 parts by weight to 70 parts by weight, such as 10 parts by weight to 20 parts by weight of the alkali and / or alkaline earth metal hydroxide.

[0321] Component (c)

[0322] In the present invention, component (c) comprises one or more oxidizing agents.

[0323] In one embodiment, component (c) comprises one or more oxidizing agents in the form of hydrogen peroxide, an organic or inorganic peroxide, molecular oxygen, ozone, air, a halogen-containing oxidizing agent, or any mixture thereof.

[0324] In the initial step of oxidation, the active radicals from the oxidant usually extract protons from the phenolic groups because this bond has the lowest dissociation energy in lignin. Since lignin has the potential to stabilize radicals through mesomeric effects, there are various pathways for the reaction to continue (but also to terminate), leading to a variety of intermediate and final products. Due to this complexity (and the conditions chosen), the average molecular weight can increase and decrease, and in their experiments, the inventors typically observed a moderate increase in the average molecular weight of about 30%.

[0325] In one embodiment, component (c) comprises hydrogen peroxide.

[0326] Hydrogen peroxide is probably the most commonly used oxidant because of its combined effects of low cost, high efficiency, and relatively low environmental impact. When hydrogen peroxide is used in the absence of a catalyst, alkaline conditions and temperature are important because the following reaction leads to radical formation:

[0327]

[0328]

[0329] It has been found that due to the oxidation process, the derivatized lignin prepared by the method according to the invention contains an increased amount of carboxylic acid groups. Without wishing to be bound by any particular theory, it is believed that the carboxylic acid group content of the oxidized lignin prepared by the method according to the invention plays an important role in the desired reaction performance of the derivatized lignin prepared by the method according to the invention.

[0330] Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. The higher hydrophilicity can enhance the solubility in water and promote adhesion to polar substrates such as mineral fibers.

[0331] Other components

[0332] In one embodiment, the method according to the invention comprises a binder and / or adhesive comprising other components, in particular component (d) in the form of an oxidation catalyst, such as one or more transition metal catalysts, such as iron sulfate, such as catalysts containing manganese, palladium, selenium, tungsten.

[0333] Such an oxidation catalyst can increase the reaction rate, thereby improving the properties of the oxidized lignin prepared by the method according to the invention.

[0334] Mass ratio of components

[0335] Those skilled in the art will use the relative amounts of components (a), (b), and (c) to achieve the desired degree of lignin oxidation.

[0336] In one embodiment,

[0337] - Component (a), comprising one or more lignins

[0338] - Component (b), comprising ammonia

[0339] - Component (c), comprising one or more oxidizing agents in the form of hydrogen peroxide

[0340] wherein, based on the dry weight of the lignin, the mass ratio of lignin, ammonia and hydrogen peroxide is such that the amount of ammonia is from 0.01 to 0.5 parts by weight, such as from 0.1 to 0.3 parts by weight, such as from 0.15 to 0.25 parts by weight of ammonia, and based on the dry weight of the lignin, the amount of hydrogen peroxide is from 0.025 to 1.0 parts by weight, such as from 0.05 to 0.2 parts by weight, such as from 0.075 to 0.125 parts by weight of hydrogen peroxide.

[0341] Process

[0342] There is more than one possibility of bringing components (a), (b) and (c) into contact to achieve the desired oxidation reaction.

[0343] In one embodiment, the method comprises the following steps:

[0344] - The step of providing component (a) in the form of an aqueous solution and / or a dispersion of one or more lignins, based on the total weight of the aqueous solution, the lignin content of the aqueous solution being from 1% to 50% by weight, such as from 5% to 25% by weight, such as from 15% to 22% by weight, such as from 18% to 20% by weight;

[0345] - The step of adjusting the pH by adding component (b) comprising an aqueous solution of ammonia, one or more amine components and / or any salts thereof;

[0346] - The oxidation step by adding component (c) comprising an oxidizing agent.

[0347] In one embodiment, the pH adjustment step is carried out such that the pH of the resulting aqueous solution and / or dispersion is ≥ 9, such as ≥ 10, such as ≥ 10.5.

[0348] In one embodiment, the pH adjustment step is carried out such that the resulting aqueous solution and / or dispersion has a pH in the range of 10.5 to 12.

[0349] In one embodiment, the pH adjustment step is carried out such that the temperature rises to ≥ 25 °C and then is controlled in the range of 25 °C to 50 °C, such as 30 °C to 45 °C, such as 35 °C to 40 °C.

[0350] In one embodiment, in the oxidation step, the temperature is raised to ≥ 35 °C and then controlled in the range of 35 °C to 150 °C, such as 40 °C to 90 °C, such as 45 °C to 80 °C.

[0351] In one embodiment, the oxidation step is carried out for a time of from 1 second to 48 hours, such as from 10 seconds to 36 hours, such as from 1 minute to 24 hours, such as from 2 hours to 5 hours.

[0352] Method II for preparing oxidized lignin

[0353] The oxidized lignin that can be used as the binder and / or binder component used in the present invention can be prepared by a method comprising contacting the following substances:

[0354] - Component (a), which comprises one or more lignins;

[0355] - Component (b), which comprises ammonia, and / or one or more amine components, and / or any salt and / or base and / or alkaline earth metal hydroxide thereof, such as sodium hydroxide and / or potassium hydroxide;

[0356] - Component (c), which comprises one or more oxidants.

[0357] - Component (d), which is in the form of one or more plasticizers.

[0358] Component (a)

[0359] Component (a) comprises one or more lignins.

[0360] In one embodiment of the method, component (a) comprises one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins obtained from a biorefining process of lignocellulosic raw materials, or any mixture thereof.

[0361] In one embodiment, component (a) comprises one or more kraft lignins.

[0362] Component (b)

[0363] In one embodiment, component (b) comprises ammonia, one or more amino components and / or any salt and / or base and / or alkaline earth metal hydroxide thereof, such as sodium hydroxide and / or potassium hydroxide.

[0364] “Ammonia-oxidized lignin” should be understood as lignin oxidized by an oxidant in the presence of ammonia. The term “ammonia-oxidized lignin” is abbreviated as AOL.

[0365] In one embodiment, component (b) comprises ammonia and / or any salt thereof.

[0366] Without wishing to be bound by any particular theory, it is believed that the improved stability of the derivatized lignin prepared according to the invention, in which component (b) is ammonia and / or any of its salts, is at least partly due to the fact that ammonia is a volatile compound and thus evaporates from the final product or can be easily removed and reused.

[0367] However, in this embodiment of the method, it is advantageous for component (b) to include a relatively small amount of a base and / or an alkaline earth metal hydroxide, such as sodium hydroxide and / or potassium hydroxide, in addition to ammonia, one or more amino components and / or any of their salts.

[0368] In some embodiments, where component (b) includes a base and / or an alkaline earth metal hydroxide, such as sodium hydroxide and / or potassium hydroxide, as a component in addition to ammonia, one or more amino components and / or any of their salts, the amount of the base and / or the alkaline earth metal hydroxide is usually small, based on ammonia, such as 5 parts by weight to 70 parts by weight, such as 10 parts by weight to 20 parts by weight of the base and / or the alkaline earth metal hydroxide.

[0369] Component (c)

[0370] In the method according to the invention, component (c) includes one or more oxidizing agents.

[0371] In one embodiment, component (c) includes one or more oxidizing agents, which are in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen-containing oxidizing agents or any mixture thereof.

[0372] In the initial step of oxidation, the active radicals from the oxidizing agent usually extract protons from the phenolic groups because this bond has the lowest dissociation energy in lignin. Since lignin has the potential to stabilize the radicals through mesomeric isomerism, there are various ways to continue (but also to terminate) the reaction and obtain various intermediate and final products. Due to this complexity (and the conditions chosen), the average molecular weight can increase and decrease, and in their experiments, we typically see a moderate increase in the average molecular weight of about 30%.

[0373] In one embodiment, component (c) includes hydrogen peroxide.

[0374] Hydrogen peroxide is probably the most commonly used oxidizing agent because of the combined effect of its low cost, high efficiency and relatively low environmental impact. When hydrogen peroxide is used in the absence of a catalyst, alkaline conditions and temperature are important because the following reaction leads to the formation of radicals:

[0375]

[0376]

[0377] It has been found that due to the oxidation process, the derivatized lignin prepared by the method according to the present invention contains an increased amount of carboxylic acid groups. Without wishing to be bound by any particular theory, it is believed that the carboxylic acid group content of the oxidized lignin prepared in the method plays an important role in the desired reactivity of the derivatized lignin prepared by the method.

[0378] Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. The higher hydrophilicity can enhance the solubility in water and promote the adhesion to polar substrates such as mineral fibers.

[0379] Component (d)

[0380] Component (d) comprises one or more plasticizers.

[0381] In one embodiment, component (d) comprises one or more plasticizers in the form of polyols, such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids 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 polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides (such as urea), or any mixture thereof.

[0382] It has been found that adding component (d) in the form of one or more plasticizers provides a reduction in the viscosity of the reaction mixture, thus allowing the production of oxidized lignin in a very effective manner.

[0383] In one embodiment, component (d) comprises one or more plasticizers in the form of polyols, such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyvinyl alcohol, acrylic polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides (such as urea), or any mixture thereof.

[0384] In one embodiment of the present invention, component (d) comprises one or more plasticizers selected from polyethylene glycol, polyvinyl alcohol, urea, or any mixture thereof.

[0385] Other components

[0386] In one embodiment, the method comprises other components, in particular component (v), which is in the form of an oxidation catalyst, such as one or more transition metal catalysts, such as iron sulfate, such as catalysts containing manganese, palladium, selenium, tungsten.

[0387] This oxidation catalyst can increase the reaction rate, thereby improving the properties of the oxidized lignin prepared by this method.

[0388] Mass ratio of components

[0389] Those skilled in the art will use the relative amounts of components (a), (b), (c) and (d) to achieve the desired degree of lignin oxidation.

[0390] In one embodiment, the implementation of the method causes the method to include:

[0391] - Component (a) includes one or more lignins;

[0392] - Component (b) includes ammonia;

[0393] - Component (c) includes one or more oxidants in the form of hydrogen peroxide;

[0394] - Component (d) includes one or more plasticizers selected from polyethylene glycol,

[0395] wherein the mass ratio of lignin, ammonia, hydrogen peroxide and polyethylene glycol is such that, based on the dry weight of lignin, the amount of ammonia is 0.01 to 0.5 parts by weight, such as 0.1 to 0.3 parts by weight, such as 0.15 to 0.25 parts by weight of ammonia (25% aqueous solution), and based on the dry weight of lignin, wherein the amount of hydrogen peroxide (30% aqueous solution) is 0.025 to 1.0 parts by weight, such as 0.07 to 0.50 parts by weight, such as 0.15 to 0.30 parts by weight of hydrogen peroxide, and wherein based on the dry weight of lignin, the amount of polyethylene glycol is 0.03 to 0.60 parts by weight, such as 0.07 to 0.50 parts by weight, such as 0.10 to 0.40 parts by weight of polyethylene glycol.

[0396] For the purposes of the present invention, the "dry weight of lignin" is preferably defined as the weight of lignin in the provided form.

[0397] Process

[0398] There is more than one possibility of bringing components (a), (b), (c) and (d) into contact to effect the desired oxidation reaction.

[0399] In one embodiment, the method includes the following steps:

[0400] - The step of providing component (a) in the form of an aqueous solution and / or a dispersion of one or more lignins, wherein the lignin content of the aqueous solution is 5% to 90% by weight, such as 10% to 85% by weight, such as 15% to 70% by weight based on the total weight of the aqueous solution;

[0401] - A step of adjusting the pH by adding component (b);

[0402] - A step of adding component (d);

[0403] - An oxidation step of adding component (c) including an oxidant.

[0404] In one embodiment, the pH adjustment step is carried out such that the pH of the resulting aqueous solution and / or dispersion is ≥9, such as ≥10, such as ≥10.5.

[0405] In one embodiment, the pH adjustment step is carried out such that the resulting aqueous solution and / or dispersion has a pH in the range of 9.5 to 12.

[0406] In one embodiment, the pH adjustment step is carried out such that the temperature rises to ≥25 °C and then is controlled in the range of 25 °C to 50 °C, such as 30 °C to 45 °C, such as 35 °C to 40 °C.

[0407] In one embodiment, in the oxidation step, the temperature is raised to ≥35 °C and then is controlled in the range of 35 °C to 150 °C, such as 40 °C to 90 °C, such as 45 °C to 80 °C.

[0408] In one embodiment, the oxidation step is carried out for a time of 1 second to 24 hours, such as 1 minute to 12 hours, such as 10 minutes to 8 hours, such as 5 minutes to 1 hour.

[0409] It has been found that the method allows for the production of a reaction mixture with a high dry matter content, so a high output can be achieved in the method, which allows the reaction product in the form of oxidized lignin to be used as a component for industrial mass-produced articles such as mineral fiber articles.

[0410] In one embodiment, the implementation of the method results in the dry matter content of the reaction mixture being 20 wt% to 80 wt%, such as 40 wt% to 70 wt%.

[0411] In one embodiment, the implementation of the method results in the oxidized lignin having a viscosity value of 100 cP to 100,000 cP, such as 500 cP to 50,000 cP, such as 1,000 cP to 25,000 cP.

[0412] For the purposes of the present invention, the viscosity is the dynamic viscosity, which is defined as the resistance of a liquid / paste to a change in shape, or the resistance of adjacent parts to movement relative to each other. The viscosity is measured in centipoise (cP), which is equivalent to 1 mPa s (millipascal second). The viscosity is measured at 20 °C using a viscometer. For the purposes of the present invention, the dynamic viscosity can be measured at 20 °C using a cone-plate Brookfield viscometer.

[0413] In one embodiment, the method is implemented such that it includes a rotor - stator device.

[0414] In one embodiment, the method is implemented such that it is carried out as a continuous or semi - continuous process.

[0415] Equipment for carrying out the method

[0416] The present invention also includes equipment for carrying out the above - mentioned method.

[0417] In one embodiment, the equipment for carrying out the method includes:

[0418] - A rotor - stator device,

[0419] - A pre - mixing device for components (a), (b), (d),

[0420] - One or more inlets for water, components (a), (b), (c) and (d),

[0421] - One or more outlets for oxidized lignin.

[0422] In one embodiment, the equipment is constructed such that the inlets for pre - mixing components (a), (b) and (d) lead to the rotor - stator device, and the equipment further includes a chamber,

[0423] said chamber having an inlet for component (c), and

[0424] said chamber having an outlet for oxidized lignin.

[0425] The rotor - stator device is a device for processing materials, including a stator configured as an inner cone with a toothed ring. The stator is used in cooperation with a rotor having arms extending from a hub. Each of these arms has teeth that engage with the teeth of the toothed ring of the stator. With each revolution of the rotor, the material to be processed is conveyed outwards by a certain distance while being subjected to strong shear effects, mixing and redistribution. The rotor arms of the upright device and the adjacent container chamber allow for the permanent rearrangement of the material from the inside to the outside and provide multiple processing of dry and / or highly viscous substances. Therefore, this device is very useful for important intensive mixing, kneading, fibrillating, decomposing and similar processes in industrial production. The upright arrangement of the housing is conducive to the material falling back from the periphery to the center of the equipment.

[0426] In one embodiment, the rotor-stator device used in the method includes a stator with a toothed ring and a rotor with teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device has the following features: a guiding funnel protrudes between the arms of the rotor, concentrating the material flow coming in from above into the central region of the container. The outer surface of the guiding funnel defines an annular gap that throttles the material flow. A feed screw is provided on the rotor to feed material into the working area of the device. The guiding funnel retains the product in the working area of the device, while the feed screw generates an increased material pressure in the central region.

[0427] For more details on the rotor-stator device used in one embodiment of the method, reference is made to US 2003 / 0042344 A1, which is incorporated herein by reference.

[0428] In one embodiment, the method is implemented such that the method uses a rotor-stator device. In this embodiment, the mixing of the components and the reaction of the components are carried out in the same rotor-stator device.

[0429] In one embodiment, the method is implemented such that the method uses two or more rotor-stator devices, where at least one rotor-stator device is used for mixing the components and at least one rotor-stator device is used for reacting the components.

[0430] The method can be divided into two steps:

[0431] 1. Prepare lignin substances (a) + (b) + (d);

[0432] 2. Oxidation of lignin substances

[0433] Generally, two different types of rotor / stator machines are used:

[0434] 1. Open rotor / stator machines, which are suitable for incorporating lignin powder into water at very high concentrations (30 wt% to 50 wt%). The mixing intensity is low, but special auxiliary equipment (inlet funnels, screws, etc.) is used to handle high-viscosity materials. The circumferential speed is low (up to 15 m / s). The machine can be used as a batch system or a continuous system.

[0435] 2. Inline rotor / stator machines, which have higher shear forces, a circumferential speed of up to 55 m / s, and create favorable conditions for very fast chemical reactions. The machines should be used continuously.

[0436] In an open rotor / stator system, a high-concentration (45 wt% to 50 wt%) lignin / water substance is prepared. The lignin powder is slowly added to warm water (30 °C to 60 °C) in which the correct amounts of aqueous ammonia and / or an alkali (alkalibase) have been added. This can be done in batch mode or the materials can be added intermittently / continuously, resulting in a continuous substance flow to the next step.

[0437] The resulting substance should be kept at a temperature of about 60 °C to keep the viscosity as low as possible so that the material can be pumped. Then the hot lignin / water substance with a pH of 9 to 12 is transferred to the oxidation step using a suitable pump such as a screw pump or other positive displacement pump.

[0438] In one embodiment, the oxidation is carried out as a continuous on-line reaction in a closed rotor / stator system. An aqueous solution of ammonia and / or an alkali is injected into the rotor / stator chamber with a metering pump at the highest turbulence / shear point. This ensures a rapid oxidation reaction. The oxidized material (AOL) leaves the on-line reactor and is collected in a suitable tank.

[0439] Reaction product

[0440] Unexpectedly, it has been found that the prepared oxidized lignins have very desirable reactive properties, while showing improved fire resistance when used in articles incorporating them into binder and / or adhesive compositions, and have improved long-term stability compared to previously known oxidized lignins.

[0441] The oxidized lignins also show improved hydrophilicity.

[0442] An important parameter for the reactivity of the prepared oxidized lignins is the carboxylic acid group content of the oxidized lignins.

[0443] In one embodiment, based on the dry weight of component (a), the carboxylic acid group content of the prepared oxidized lignin is from 0.05 mmol / g to 10 mmol / g, such as from 0.1 mmol / g to 5 mmol / g, such as from 0.20 mmol / g to 2.0 mmol / g, such as from 0.40 mmol / g to 1.5 mmol / g, such as from 0.45 mmol / g to 1.0 mmol / g.

[0444] Another way to describe the carboxylic acid group content is to use the average carboxylic acid group content per lignin macromolecule according to the following formula:

[0445]

[0446] In one embodiment, in the prepared oxidized lignin, the average carboxylic acid group content per macromolecule of component (a) is more than 1.5 groups, such as more than 2 groups, such as more than 2.5 groups.

[0447] Method III for preparing oxidized lignin

[0448] The oxidized lignin used as a component of the binder and / or adhesives in the present invention can be prepared by a method comprising contacting:

[0449] - Component (a), which comprises one or more lignins;

[0450] - Component (b), which comprises ammonia, and / or one or more amine components, and / or any salts thereof, and / or bases and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide;

[0451] - Component (c), which comprises one or more oxidants,

[0452] - Optional component (d), which is in the form of one or more plasticizers,

[0453] and performing a mixing / oxidation step, in which an oxidation mixture is produced, followed by an oxidation step in which the oxidized mixture is allowed to react for a residence time of from 1 second to 10 hours, such as from 10 seconds to 6 hours, such as from 30 seconds to 2 hours.

[0454] Components (a), (b), (c) and (d) are as defined above in Method II for preparing oxidized lignin.

[0455] In one embodiment of the present invention, the method comprises a premixing step of contacting the components with each other.

[0456] In the premixing step, the following components can be contacted with each other:

[0457] - Component (a) and component (b), or

[0458] - Component (a) and component (b) and component (c), or

[0459] - Component (a) and component (b) and component (d), or

[0460] - Component (a) and component (b) and component (c) and component (d).

[0461] In an embodiment of the present invention, the premixing step can be carried out as a separate step, and the mixing / oxidation step is carried out after the premixing step. In such an embodiment of the present invention, it is particularly advantageous to contact component (a) and component (b) and optionally component (d) in the premixing step. In the subsequent mixing / oxidation step, component (c) is then added to the premix produced in the premixing step.

[0462] In another embodiment of the present invention, the premixing step may correspond to the mixing / oxidation step. In this embodiment of the present invention, components such as component (a), component (b), and component (c) are mixed and the oxidation process starts simultaneously. The subsequent residence time may be carried out in the same equipment used to carry out the mixing / oxidation step. If component (c) is air, this embodiment of the present invention is particularly advantageous.

[0463] It has been found that by following the mixing / oxidation step with an oxidation step, where the reaction mixture is preferably not further mixed, the oxidation rate can be controlled in a very effective manner. At the same time, since the oxidation step following the mixing / oxidation step requires less complex equipment, the cost of carrying out the method is reduced.

[0464] Another advantage is that the oxidized lignin produced is particularly stable. Another unexpected advantage is that the oxidized lignin produced can be well adjusted in terms of viscosity. Another unexpected advantage is that the concentration of the oxidized lignin can be very high.

[0465] In one embodiment, the residence time is selected such that the oxidation reaction proceeds to the desired degree of completion, preferably to complete completion.

[0466] System I for carrying out Method III

[0467] In one embodiment, the system for carrying out the method comprises:

[0468] - at least one rotor-stator device,

[0469] - one or more inlets for water and components (a) and (b),

[0470] - one or more outlets of the rotor-stator device,

[0471] - at least one reaction device, in particular at least one reaction tube, which is arranged downstream of at least one or more outlets in the process flow direction.

[0472] In one embodiment, the system comprises one or more inlets for component (c) and / or component (d).

[0473] In one embodiment, the system comprises a premixing device.

[0474] The premixing device may comprise one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0475] In one embodiment, the premixing device comprises inlets for water and components (a) and (b).

[0476] In the premixing step, component (c) may also be mixed with the three mentioned components (water, component (a) and component (b)). Then, the premixing device may have an additional inlet for component (c). If component (c) is air, the premixing device may be formed by an open mixing container, so in this case, component (c) has contacted the other components (water, component (a) and component (b)) through the opening of the container. Also in this embodiment of the present invention, the premixing device may optionally include an inlet for component (d).

[0477] In one embodiment, the system is constructed in such a way that:

[0478] The inlets for components (a), (b) and (d) are inlets of the premixing device, in particular inlets of an open rotor - stator device,

[0479] whereby the system also includes an additional rotor - stator device,

[0480] The additional rotor - stator device has an inlet for component (c) and the additional rotor - stator device has an outlet for oxidized lignin.

[0481] The premixing step and the mixing / oxidation step can be carried out simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device, namely the rotor - stator device.

[0482] In one embodiment, a rotor - stator device for the method according to the present invention includes a stator having a toothed ring and a rotor having teeth meshing with the teeth of the stator. In this embodiment, the rotor - stator device has the following features: a guiding funnel projects between the arms of the rotor, concentrating the material flow coming in from above into the central area of the container. The outer surface of the guiding funnel defines an annular gap that throttles the material flow. A feed screw is provided on the rotor to feed material into the working area of the device. The guiding funnel retains the product in the working area of the device, while the feed screw generates an increased material pressure in the central area.

[0483] System II for performing Method III

[0484] In one embodiment, the system for performing the method includes:

[0485] - one or more inlets for water, component (a) and (b),

[0486] - at least one mixing and oxidation device having one or more outlets, and

[0487] - at least one mixer / heat exchanger arranged downstream of at least one or more outlets in the process flow direction, whereby the mixer / heat exchanger includes temperature control means.

[0488] In one embodiment, the system includes one or more additional inlets for component (c) and / or component (d).

[0489] In one embodiment, the system includes a premixing device.

[0490] The premixing device may include one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0491] In one embodiment, the premixing device includes inlets for water, component (a), and component (b).

[0492] In the premixing step, component (c) may also be mixed with the three mentioned components (water, component (a), and component (b)). Then, the premixing device may have an additional inlet for component (c). If component (c) is air, the premixing device may be formed by an open mixing container, so in this case, component (c) has contacted the other components (water, component (a), and component (b)) through the opening of the container. Also in this embodiment of the present invention, the premixing device may optionally include an inlet for component (d).

[0493] In one embodiment, the system is constructed in such a way that the inlets for components (a), (b), and (d) are inlets of an open rotor-stator device, whereby the system further includes a mixer / heat exchanger having an inlet for component (c) and an outlet for oxidized lignin.

[0494] The premixing step and the mixing / oxidation step can be carried out simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device.

[0495] In one embodiment, a rotor-stator device for the method of the present invention includes a stator having a toothed ring and a rotor having teeth meshing with the teeth of the stator. In this embodiment, the rotor-stator device has the following features: a guiding funnel projects between the arms of the rotor, concentrating the material flow coming from above into the central region of the container. The outer surface of the guiding funnel defines an annular gap that throttles the material flow. A feed screw is provided on the rotor to feed material into the working area of the device. The guiding funnel retains the product in the working area of the device, while the feed screw generates an increased material pressure in the central region.

[0496] Of course, other devices can also be used as the premixing device. In addition, the premixing step can be carried out in the mixing and oxidation device.

[0497] In one embodiment, the mixing and oxidation device is a static mixer. A static mixer is a device for continuously mixing fluid materials without moving components. One design of a static mixer is a plate mixer, and another common type of device consists of mixer elements contained within a cylindrical (tube) or square housing.

[0498] In one embodiment, the mixer / heat exchanger is configured as a multi-tube heat exchanger with mixing elements. The mixing elements are preferably fixed devices through which the mixture must flow and thereby mix as a result of the flow. The mixer / heat exchanger can be configured as a plug flow reactor.

[0499] Example I

[0500] Example IA – Oxidation of lignin with hydrogen peroxide in aqueous ammonia solution:

[0501] The amounts of ingredients used according to Example IA are provided in Tables IA 1.1 and IA 1.2.

[0502] Although sulfate lignin is soluble in water at relatively high pH values, it is known that at a certain weight percentage, the viscosity of the solution increases sharply. It is generally believed that the increase in viscosity is due to the combined effect of strong hydrogen bonding and π - electron interactions of the many aromatic rings present in lignin. For sulfate lignin, a sudden increase in viscosity in water is observed at about 21 wt% to 22 wt%, and 19 wt% of sulfate lignin was used in the examples.

[0503] In the pH adjustment step, an aqueous ammonia solution is used as the base. The amount is fixed at 4 wt% based on the total reaction weight. The pH value after the pH adjustment step and at the start of oxidation is 10.7.

[0504] Table IA2 shows the CHNS elemental analysis results of sulfate lignin before and after oxidation. Before analysis, the samples were heat - treated at 160 °C to remove adsorbed ammonia. The analysis shows that during the oxidation process, a certain amount of nitrogen becomes part of the oxidized lignin structure.

[0505] In the tests of the batch experiments, it was determined that adding the total amount of hydrogen peroxide in small time intervals is beneficial for oxidation rather than adding peroxide in small amounts over a long period. 2.0 wt% of H2O2 based on the total reaction weight was used in this example.

[0506] Oxidation is an exothermic reaction, and an increase in temperature is noted after adding the peroxide. In this example, the temperature was maintained at 60 °C for three hours of the reaction.

[0507] After oxidation, the amount of lignin functional groups per gram of sample increases, as shown by 31P NMR and water titration method. 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) was used as phosphorylation reagent and cholesterol was used as internal standard to prepare 31 P NMR samples. The NMR spectra of kraft lignin before and after oxidation were analyzed and the results are summarized in Table IA3.

[0508] The change in COOH groups was determined by water titration and using the following formula:

[0509]

[0510] Where V 2s and V 1s is the endpoint volume of the sample, and V 2b and V 1b is the volume of the blank. In this case, C 酸 is 0.1M HCI, m s is the weight of the sample. The values ​​obtained by water titration before and after oxidation are shown in Table IA4.

[0511] The average COOH functionality can also be quantified by the saponification value, which expresses the number of milligrams of KOH required to saponify 1 g of lignin. This method can be found in AOCS Official Method Cd 3-25.

[0512] The average molecular weight was determined before and after oxidation using a PSS PolarSil column (9:1 (v / v) dimethyl sulfoxide / water eluent, 0.05 M LiBr) and a UV detector at 280 nm. The combination of COOH concentration and average molecular weight also enabled the calculation of the average carboxylic acid group content per lignin macromolecule, and these results are shown in Table IA5.

[0513] Example IB – Scale-up of lignin oxidation in ammonia by hydrogen peroxide to pilot scale

[0514] The oxidation of lignin with hydrogen peroxide is an exothermic process and even at laboratory scale, a significant temperature increase was observed after the addition of peroxide. This is a natural consideration when scaling up chemical processes, since the heat generated is related to the cubic dimension (volume), while cooling generally only increases with the square dimension (area). Furthermore, due to the high viscosity of the adhesive intermediates, the process equipment must be carefully selected or designed. Therefore, the scale-up is carefully designed and carried out in several steps.

[0515] The first scale-up step was from 1 L (laboratory scale) to 9 L using a stainless-steel professional mixer supplemented with very efficient mechanical mixing. The final temperature after scale-up was only slightly higher than the laboratory scale, which was attributed to the efficient air cooling of the reactor and the slow addition of hydrogen peroxide.

[0516] The next scale-up step was carried out in a closed 200 L reactor with an efficient water jacket and an efficient propeller stirrer. This time the scale was 180 L, and hydrogen peroxide was added in two steps. The separation was about 30 minutes. This scale-up was relatively smooth, although a considerable amount of foam was a problem, partly due to the high reactor filling. To control foaming, a small amount of food-grade antifoaming agent was sprayed on the foam. Most importantly, external water cooling was used to obtain a temperature-controlled final temperature below 70 °C.

[0517] The pilot-scale reaction was carried out in an 800 L reactor with a water-cooled jacket and a two-blade propeller stirrer. 158 kg of lignin (UPM LignoBoost TM BioPiva 100) with a dry matter content of 67 wt% was crushed and suspended in 224 kg of water and stirred to form a homogeneous suspension. With continuous stirring, 103 kg of 25% ammonia water was pumped into the reactor and stirred for another 2 hours to form a dark and viscous lignin solution.

[0518] 140 kg of 7.5 wt% hydrogen peroxide was added to the stirred lignin solution within 15 minutes at 20 °C to 25 °C. During and after the addition of hydrogen peroxide and cooling water to the cooling jacket, the temperature and foam level were carefully monitored to maintain an acceptable foam level, a temperature rise of less than 4 °C per minute, and a final temperature below 70 °C. After the temperature rise stopped, the cooling was turned off, and the product mixture was stirred for another 2 hours and then transferred to a transport container.

[0519] Based on the scale-up runs, it can be concluded that even though the reaction is exothermic, in fact most of the reaction heat is balanced by the heat capacity of water from room temperature to about 60 °C, and only the last part has to be removed by cooling. It should be noted that because of this and because of the short reaction time, this process is very suitable for scale-up and process intensification using continuous reactors such as in-line mixers, tubular reactors, or CSTR-type reactors. This will ensure good temperature control and a more defined reaction process.

[0520] Tests on the scale-up batches showed that the produced oxidized lignin had properties consistent with the laboratory-produced batches.

[0521] Table IA 1.1

[0522] Quantities of materials used in the provided form:

[0523]

[0524] Table IA 1.2

[0525] Dosage of active material:

[0526]

[0527] Table IA 2

[0528] Elemental analysis of kraft lignin before and after oxidation:

[0529]

[0530] Table IA 3

[0531] By 31 P-NMR to obtain the functional group distribution of kraft lignin before and after oxidation:

[0532]

[0533] Table IA 4

[0534] COOH group content (mmol / g) determined by water titration:

[0535]

[0536] Table IA5

[0537] Table IA5. Number-average molar mass (Mn) and weight-average molar mass (Mw) determined by size-exclusion chromatography, expressed in g / mol, and the average carboxylic acid group content per lignin macromolecule before and after oxidation.

[0538]

[0539] Example II

[0540] In the following examples, several kinds of oxidized lignins were prepared. The following properties of the oxidized lignins were determined:

[0541] Component solids content:

[0542] The content of each component in a given oxidized lignin solution is based on the anhydrous mass of the component or as described below.

[0543] Kraft lignin is from UPM as BioPiva100 TMSupplied as dry powder. NH4OH 25% was provided by Sigma - Aldrich and used in the supplied form. H2O2, 30% (Cas no 7722 - 84 - 1) was provided by Sigma - Aldrich and used in the supplied form or diluted with water. PEG 200 was provided by Sigma - Aldrich, assumed anhydrous for simplicity and used as received. PVA (Mw 89,000 - 98,000, Mw 85,000 - 124,000, Mw 130,000, Mw 146,000 - 186,000) (Cas no 9002 - 89 - 5) was provided by Sigma - Aldrich, assumed anhydrous for simplicity and used as received. Urea (Cas no 57 - 13 - 6) was provided by Sigma - Aldrich and used in the supplied form or diluted with water. Glycerol (Cas no 56 - 81 - 5) was provided by Sigma - Aldrich, assumed anhydrous for simplicity and used as received.

[0544] Oxidized lignin solid

[0545] The content of oxidized lignin after heating to 200 °C for 1 hour is called "dry solid matter" and is expressed as a percentage of the remaining weight after heating.

[0546] Disc - shaped rock wool samples (diameter: 5 cm; height 1 cm) were cut out from the rock wool and heat - treated at 580 °C for at least 30 minutes to remove all organic matter. The solids of the binder mixture were measured by distributing a sample (about 2 g) of the binder mixture onto the heat - treated rock wool disc in a foil container. The weight of the foil container with the rock wool disc was weighed directly before and after adding the binder mixture. Two such binder - mixture - loaded rock wool discs were produced in the foil container and then heated at 200 °C for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the dry solid matter was calculated as the average of the two results.

[0547] COOH group content

[0548] The change in the COOH group content was also determined by titration with water and using the following formula:

[0549]

[0550] where V 2s and V 1s are the end - point volumes of the sample, and V 2b and V 1b are the volumes of the blank control samples. In this case, C 酸 is 0.1 M HCI, and m s,g is the weight of the sample.

[0551] Method for manufacturing oxidized lignin:

[0552] 1) During the stirring process, water and lignin are mixed in a water bath at room temperature (20 °C to 25 °C) in a 3-neck glass-bottom flask connected to a condenser and a temperature recording device. Stir for 1 hour.

[0553] 2) Ammonia is added in 1 portion during the stirring process.

[0554] 3) If the slightly exothermic reaction with ammonia does not raise the temperature, heat to raise the temperature to 35 °C.

[0555] 4) Measure the pH value.

[0556] 5) Add the plasticizer PEG200 and stir for 10 minutes.

[0557] 6) Approximately 1 hour after the lignin is completely dissolved, slowly add 30% H2O2 all at once.

[0558] 7) The exothermic reaction upon adding H2O2 raises the temperature in the glass-bottom flask. If the reaction temperature is below 60 °C, raise the temperature to 60 °C and let the sample stand at 60 °C for 1 hour.

[0559] 8) Then remove the round-bottom flask from the water bath and cool it to room temperature.

[0560] 9) Take out the sample and measure the dry solid matter, COOH, viscosity, density, and pH value.

[0561] Oxidized lignin composition

[0562] In the following text, the entry numbers of the oxidized lignin examples correspond to the entry numbers used in Table II.

[0563] Example IIA

[0564] Dissolve 71.0 g of lignin UPM Biopiva 100 in 149.0 g of water at 20 °C, add 13.3 g of 25% NH4OH and stir for 1 hour using a magnetic stirrer, after which 16.8 g of 30% H2O2 is slowly added during the stirring process. Raise the temperature to 60 °C in a water bath. After oxidizing for 1 hour, cool the water bath to stop the reaction. Analyze the resulting material for COOH, dry solid matter, pH, viscosity, and density.

[0565] Example IIE

[0566] 71.0 g of lignin UPM Biopiva 100 was dissolved in 88.8 g of water at 20 °C. 13.3 g of 25% NH4OH was added and stirred for 1 hour using a magnetic stirrer. 22.8 g of PEG 200 was added and stirred for 10 minutes, after which 16.7 g of 30% H2O2 was slowly added during stirring. The temperature was raised to 60 °C in a water bath. After oxidizing for 1 hour, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solid matter, pH, viscosity, and density.

[0567] Example IIC

[0568] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20 °C. 13.3 g of 25% NH4OH was added and stirred for 1 hour using a mechanical stirrer, after which 16.6 g of 30% H2O2 was slowly added during stirring. The temperature was raised to 60 °C in a water bath. After oxidizing for 1 hour, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solid matter, pH, viscosity, and density.

[0569] Example II F

[0570] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20 °C. 13.3 g of 25% NH4OH was added and stirred for 1 hour using a mechanical stirrer. 19.0 g of PEG 200 was added and stirred for 10 minutes, after which 16.6 g of 30% H2O2 was slowly added during stirring. The temperature was raised to 60 °C in a water bath. After oxidizing for 1 hour, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solid matter, pH, viscosity, and density.

[0571]

[0572]

[0573]

[0574]

[0575] Example III:

[0576] 8.5 L of hot water (50 °C) and 1.9 L of NH4OH (24.7%) were mixed, and 9.0 kg of lignin (UPM biopiva100) was slowly added within 10 minutes under high stirring (660 rpm, 44 Hz).

[0577] The temperature increases due to high shear force. After 30 minutes, 4 L of hot water is added, and the material is stirred for another 15 minutes before adding the remaining hot water (5 L). Samples are taken and the undissolved lignin is analyzed by using a Hegman gauge and pH measurement.

[0578] Then the premix is transferred to a rotor-stator device and a reaction device, where oxidation is carried out by using H2O2 (17.5 vol%). The reaction device used in this case has at least a reaction tube and a reaction vessel in part. The feeding rate of the premix is 150 L / h, and the feeding rate of H2O2 is 18 L / h.

[0579] In this example, a Cavitron CD1000 rotor-stator device is used for the mixing / oxidation step. The rotor-stator device operates at 250 Hz (circumferential speed of 55 m / s), and the back pressure is 2 bar. The residence time in the reaction tube is 3.2 minutes, and the residence time in the reaction vessel is 2 hours.

[0580] The temperature of the premix is 62 °C, and the oxidation step raises the temperature to 70 °C.

[0581] Analyze the COOH group content, dry solid matter, pH, viscosity, and residual H2O2 of the final product.

[0582] Table III:

[0583]

[0584] Example IV:

[0585] Mix 484 L of hot water (70 °C) and 47.0 L of NH4OH (24.7%), and then slowly add 224.0 kg of lignin (UPM biopiva 100) within 15 minutes under high stirring. Samples are taken and the undissolved lignin is analyzed by using a Hegman gauge and pH measurement.

[0586] Then the premix is transferred to a static mixer and a mixer / heat exchanger, where oxidation is carried out by using H2O2 (35 vol%). The feeding rate of the premix is 600 L / h, and the feeding rate of H2O2 is 17.2 L / h. The residence time in the mixer / heat exchanger is 20 minutes.

[0587] During the oxidation step, the temperature of the mixture rises up to 95 °C.

[0588] Analyze the COOH group content, dry solid matter, pH, viscosity, and residual H2O2 of the final product.

[0589] Preparation of the binder based on this AOL: 49.3 g of AOL (19.0% solids), 0.8 g of primid XL552 (100% solids), and 2.4 g of PEG200 (100% solids) were mixed with 0.8 g of water to produce 19% solids; then it was used for the mechanical property test in the bar test.

[0590]

[0591] Bar test

[0592] The mechanical strength of the binder was tested in the bar test. For each binder, 16 bars were made from a mixture of the binder and rock wool pellets from rock wool spinning production.

[0593] A sample (16.0 g) of the binder solution containing 15% dry solids was thoroughly mixed with the pellets (80.0 g). Then the resulting mixture was filled into four slots provided in the form of heat-resistant silica gel for making small bars (4×5 slots for each shape; top size of the slot: length = 5.6 cm, width = 2.5 cm; bottom size of the slot: length = 5.3 cm, width = 2.2 cm; height of the slot = 1.1 cm). Then the mixture placed in the slots was pressed with a flat metal bar of appropriate size to produce a uniform bar surface. 16 bars for each binder were made in this way. Then the resulting bars were cured at 200 °C. The curing time was 1 hour. After cooling to room temperature, the bars were carefully removed from the container. 5 of the bars were aged in an 80 °C water bath for 3 hours.

[0594] After drying for 1 to 2 days, the aged bars and 5 unaged bars were fractured in a three-point bending test (test speed: 10.0 mm / min; degree of fracture: 50%; nominal strength: 30 N / mm 2 ; support distance: 40 mm; maximum deflection 20 mm; nominal electronic module body 10000 N / mm 2 ) and their mechanical strength was studied on a Bent Tram machine. When placing the bars in the machine, the "top surface"

[0595] (i.e., the surface with dimensions length = 5.6 cm and width = 2.5 cm) was facing up.

[0596] Description of the drawings

[0597] Figure 1 Shows a part of the possible lignin structure.

[0598] Figure 2 Shows lignin precursors and common inter-unit linkages.

[0599] Figure 3Shows at least four groups of industrial lignin available on the market.

[0600] Figure 4 Shows a summary of some industrial lignin properties.

[0601] Figure 5 Is a perspective view of an insulating product according to the present invention;

[0602] Figure 6 Is a schematic view of the method of the present invention before the curing furnace stage. Detailed Description

[0603] Figure 5 Shows an insulating product 1 formed by an MMVF batt 2. At its bottom, the batt is provided with a first facing 3. The first facing 3 may have moisture-proof properties. The facing 3 is connected to the MMVF batt 2 by an adhesive layer 4. In this specific embodiment, although not necessary in the present invention, on its top side, the MMVF batt 2 is provided with an adhesive layer 5. The adhesive layer 5 is used to fix the insulating product to the object to be insulated. For ease of storage and transportation, a removable second facing 6 of a heat-stable silicone material is provided on the adhesive layer 5. It should be noted here that the adhesive layer extends a short distance from the edge of the insulating product to facilitate the removal of the cover plate.

[0604] The manufacture of such an insulating product can be carried out as follows, as Figure 6 shown.

[0605] The MMVF batt 2 is made by air-laying an MMVF web with an adhesive and consolidating it (not shown). Starting from the MMVF batt 2 supplied via a conveyor belt formed by a roller 7, a certain amount of adhesive is first supplied by an atomizing device 11 provided with nozzles and sprayed in the form of an aqueous composition defined by the present invention onto the first facing 3 provided by the roller. In this case, the roller is flexible and can take the form of, for example, a layer of woven or non-woven fiberglass gauze, fabric, foil, plastic, or a combination thereof. The first facing 3 is arranged on the lower side of the MMVF batt 2 by means of a roller 10.

[0606] Subsequently, a second facing layer 6 in the form of a heat-stable polysiloxane PE foil is provided on the upper side of the MMVF batt 2 by a roller 9. As described for the facing layer 3, and again starting from the MMVF batt 2 supplied via the conveyor belt of the roller 7, the adhesive 4 of the adhesive layer 5 for fixing the insulating product to the object to be insulated is applied to the main surface of the batt 2 by a spraying device 8.

[0607] Subsequently, the MMVF batt is cured in a conventional manner by passing it through a curing furnace (not shown) for the adhesive for the first facing 3 and the adhesive for the MMVF matrix.

[0608] Example

[0609] Tests were conducted to determine the peel strength of the fiberglass scrim applied to the MMVF acoustic element using the adhesive of claim 1. The insulation product is an insulation product for a flat-top insulation product having the properties defined in Table 1 below:

[0610] Table 1

[0611]

[0612] The determination of the LOI (adhesive content) was carried out according to DS / EN13820:2003 for the determination of the organic content, where the adhesive content is defined as the amount of organic material burned off at a given temperature, here using (590 ± 20 °C) for at least 10 minutes or longer until the mass is constant. The determination of the loss on ignition consists of at least 10 g of mineral wool, corresponding to 8 to 20 incisions (at least 8 incisions), evenly distributed on the specimen using a cork borer, ensuring that the entire product thickness is included.

[0613] The peel strength was determined as follows:

[0614] The scrim adhesion was measured using a 5 cm wide metal punch and a small manual weight with a hook [g].

[0615] Measurement method:

[0616] Place the product on a flat and even surface,

[0617] Using a cutter, cut the surface of the scrim into a length of approximately 50 cm,

[0618] Connect the torn end to the grip of the dynamometer and pull.

[0619] At the same time, the maximum and minimum scale deflections should be read.

[0620] Results

[0621]

[0622]

[0623] It is generally considered that commercial production requires a peel strength of at least 100 g. It can be seen that the products of the present invention fully meet this standard.

[0624] Details of the adhesive composition:

[0625] 3267 kg of water is charged into a 6000 L reactor, and then 287 kg of ammonia water (24.7%) is charged. Then 1531 kg of lignin UPM BioPiva 100 is slowly added within 30 to 45 minutes. The mixture is heated to 40 °C and held at this temperature for 1 hour. After 1 hour, the insoluble lignin is inspected. This can be achieved by examining the solution on a glass plate or a Hegman gauge. The visible insoluble lignin is small particles in the brown binder. During the dissolution step, the color of the lignin solution will change from brown to shiny black.

[0626] After the lignin is completely dissolved, 1 liter of foam inhibitor (Skumdaemper 11-10 from is added. The temperature of the batch is maintained at 40 °C.

[0627] Then the addition of 307.5 kg of 35% hydrogen peroxide is started. The hydrogen peroxide is fed at a rate of 200 liters / hour to 300 liters / hour. The first half of the hydrogen peroxide is added at a rate of 200 liters / hour, and then the feed rate is increased to 300 liters / hour.

[0628] During the addition of hydrogen peroxide, the temperature in the reaction mixture is controlled by heating or cooling so that the final reaction temperature reaches 65 °C.

[0629] After reacting at 65 °C for 15 minutes, the reaction mixture is cooled to a temperature below 50 °C. A resin with a COOH value of 1.2 mmol / g solid is thus obtained.

[0630] Starting from this ammonia-oxidized lignin (AOL) resin, a binder is formulated by adding 270 kg of polyethylene glycol 200 and an aqueous solution of 281 kg of 31% Primid XL-552 (β-hydroxyalkylamide).

Claims

1. A method of manufacturing an insulating product, the method comprising: Provided is a man - made vitreous fiber mat in a matrix containing a binder, wherein the man - made vitreous fiber mat includes at least one major surface; Provided is a facing; Fixing the facing to at least one major surface of the man - made vitreous fiber mat by using an adhesive, wherein the adhesive is an aqueous adhesive composition, and the aqueous adhesive composition includes: - Component i, which is in the form of one or more oxidized lignins, - Component ii, which is in the form of one or more cross - linkers, and - Component iii, which is in the form of one or more plasticizers, and Curing the adhesive to provide a cross - linked adhesive.

2. The method according to claim 1, wherein the facing is selected from woven fiberglass fabric, non-woven fiberglass fabric, cheesecloth, rovings, and spunbond polyester fiber web.

3. The method according to claim 1, wherein the facing is selected from woven fiberglass scrim and non-woven fiberglass scrim.

4. The method according to claim 1, wherein the facing is selected from fiberglass filament fabric.

5. The method according to claim 1, wherein the facing is selected from glass filament fabric.

6. The method according to claim 1, wherein the facing is selected from gas-phase film, moisture barrier layer, roof lining foil, and home decoration.

7. The method according to claim 1, wherein the facing is non-woven fiberglass scrim having an areal weight in the range of 30 g / m 2 to 150 g / m 2 range.

8. The method according to claim 1, wherein the facing is non-woven fiberglass scrim having a mineral coating, and having an areal weight in the range of 150 g / m 2 to 350 g / m 2 range.

9. The method according to claim 1, wherein the facing is fiberglass filament fabric having an areal weight in the range of 90 g / m 2 to 180 g / m 2 range.

10. The method according to claim 1, wherein the facing is glass filament fabric having an areal weight in the range of 90 g / m 2 to 180 g / m 2 range.

11. The method according to any one of claims 1-10, wherein the facing has at least one major surface, and the method comprises applying an adhesive to the major surface of the facing and / or the artificial vitreous fiber batt, and then applying the major surface of the facing to the major surface of the artificial vitreous fiber batt.

12. The method according to any one of claims 1 - 10, comprising applying the binder by spraying.

13. The method according to any one of claims 1 - 10, wherein the curing step of the binder is carried out at a temperature of 100 °C to 300 °C.

14. The method according to claim 13, wherein the curing step of the binder is carried out at a temperature of 170 °C to 270 °C.

15. The method according to claim 13, wherein the curing step of the binder is carried out at a temperature of 180 °C to 250 °C.

16. The method according to claim 13, wherein the curing step of the binder is carried out at a temperature of 190 °C to 230 °C.

17. The method according to any one of claims 1 - 10, wherein when the binder for the man - made vitreous fibres is uncured, the step of fixing the facing to at least one major surface of the man - made vitreous fibre batt is carried out, and the step of curing the binder also cures the binder in the man - made vitreous fibre substrate.

18. The method according to any one of claims 1 - 10, wherein the step of fixing the facing to at least one major surface of the man - made vitreous fibre batt is carried out after the binder of the man - made vitreous fibres has cured.

19. The method according to any one of claims 1 - 10, wherein the density of the man - made vitreous fibre batt is in the range of 20 kg / m 3 to 200 kg / m 3 range.

20. The method according to any one of claims 1 - 10, wherein the loss on ignition of the man - made vitreous fibre batt bonded by the binder is in the range of 0.5 wt% to 8 wt%.

21. The method according to claim 20, wherein the loss on ignition of the man - made vitreous fibre batt bonded by the binder is in the range of 2 wt% to 5 wt%.

22. The method according to any one of claims 1 - 10, wherein the thickness of the insulation product is in the range of 20 mm to 400 mm.

23. The method according to any one of claims 1 - 10, wherein the application amount of the binder is 40 g / m2 to 400 g / m2 of liquid binder.

24. The method according to claim 23, wherein the application amount of the binder is 50 g / m2 to 200 g / m2 of liquid binder.

25. The method according to claim 23, wherein the application amount of the binder is 60 g / m2 to 150 g / m2 of liquid binder.

26. The method according to any one of claims 1 - 10, wherein the method further comprises applying a coating to the facing after fixing the facing to the vitreous synthetic fiber batt.

27. The method according to any one of claims 1 - 10, wherein the insulation product is selected from indoor ceiling insulation products, interior wall insulation products, or roof insulation products.

28. The method according to any one of claims 1 - 10, wherein the insulation product is selected from exterior facades, ventilated facades, ventilation ducts, or acoustic products for channels.

29. The method according to any one of claims 1 - 10, wherein the binder in the vitreous synthetic fiber batt is a binder composition, which is an aqueous binder composition before curing, and the aqueous binder composition comprises: - Component i, which is in the form of one or more oxidized lignins; - Component ii, which is in the form of one or more cross - linkers; - Component iii, which is in the form of one or more plasticizers.

30. A method of manufacturing an insulation product, the method comprising: Provided is a man - made vitreous fiber mat in a matrix containing an uncured binder, wherein the man - made vitreous fiber mat includes at least one major surface; Provided is a facing; Applying the facing to at least one major surface of the man - made vitreous fiber mat; and curing the binder to provide a cross - linked binder for fixing the facing to the major surface, wherein before curing, the binder is an aqueous binder composition, and the aqueous binder composition includes: - Component i, which is in the form of one or more oxidized lignins; - Component ii, which is in the form of one or more cross - linkers; - Component iii, which is in the form of one or more plasticizers.

31. The method according to claim 30, wherein the step of curing the binder is carried out at a temperature of 100°C to 300°C.

32. The method according to claim 31, wherein the step of curing the binder is carried out at a temperature of 170°C to 270°C.

33. The method according to claim 31, wherein the step of curing the binder is carried out at a temperature of 180°C to 250°C.

34. The method according to claim 31, wherein the step of curing the binder is carried out at a temperature of 190°C to 230°C.

35. The method according to claim 1 or 30, wherein component i is in the form of one or more ammonia - oxidized lignins.

36. The method according to claim 1 or 30, wherein component ii comprises one or more cross - linkers selected from β - hydroxyalkylamide cross - linkers and / or oxazoline cross - linkers.

37. The method according to claim 1 or 30, wherein component ii comprises: - One or more cross - linkers selected from polyethyleneimine, polyvinylamine, fatty amines; and / or - One or more cross - linkers in the form of fatty acid amides; and / or - One or more cross - linkers selected from dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid; and / or - One or more cross - linkers selected from polyester polyols; and / or - One or more cross - linkers selected from starch, modified starch, CMC; and / or - One or more cross - linkers in the form of aliphatic polyfunctional carbodiimides; and / or - One or more cross - linkers selected from melamine - type cross - linkers.

38. The method according to claim 37, wherein the polyester polyol is polycaprolactone.

39. The method according to claim 37, wherein the melamine crosslinking agent is a hexakis(methylmethoxy)melamine crosslinking agent.

40. The method according to claim 1 or 30, wherein based on the dry weight of component i, the aqueous adhesive and / or binder composition comprises component ii in an amount of from 1 wt% to 40 wt%.

41. The method according to claim 40, wherein based on the dry weight of component i, the aqueous adhesive and / or binder composition comprises component ii in an amount of from 4 wt% to 20 wt%.

42. The method according to claim 40, wherein based on the dry weight of component i, the aqueous adhesive and / or binder composition comprises component ii in an amount of from 6 wt% to 12 wt%.

43. The method according to claim 1 or 30, wherein component iii comprises one or more plasticizers selected from polyethylene glycol, polyethers, hydrogenated sugars, phthalates, acids, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, and / or lactides.

44. The method according to claim 43, wherein the acid is: adipic acid, vanillic acid, lactic acid, and / or ferulic acid.

45. The method according to claim 43, wherein the polyether is polyethylene glycol ether.

46. The method according to claim 43, wherein the acrylic polymer is an acrylic polymer having free carboxyl groups.

47. The method according to claim 43, wherein the polyurethane dispersion is a polyurethane dispersion having free carboxyl groups.

48. The method according to claim 1 or 30, wherein component iii comprises: - One or more plasticizers selected from fatty alcohols, monohydroxy alcohols; and / or - One or more plasticizers selected from alkoxylates; and / or - One or more plasticizers in the form of propylene glycol; and / or - One or more plasticizers in the form of ethylene glycol esters; and / or - One or more plasticizers selected from adipates, acetates, benzoates, cyclohexanecarboxylates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates; and / or - One or more plasticizers selected from phenolic derivatives; and / or - One or more plasticizers selected from silanols, siloxanes; and / or - One or more plasticizers selected from sulfates, sulfonates and / or phosphates; and / or - One or more plasticizers in the form of hydroxy acids; and / or - One or more plasticizers selected from monomeric amides, benzamides, fatty acid amides; and / or - One or more plasticizers selected from quaternary ammonium compounds; and / or - One or more plasticizers selected from vegetable oils; and / or - One or more plasticizers selected from hydrogenated oils, acetylated oils; and / or - One or more plasticizers selected from acidic methyl esters; and / or - One or more plasticizers selected from alkyl polyglycosides, glucamides, aminoglucamides, sucrose esters, sorbitan esters; and / or - One or more plasticizers selected from polyethylene glycol, polyethylene glycol ethers.

49. The method according to claim 48, wherein the monohydroxy alcohol is pentanol or stearyl alcohol.

50. The method according to claim 48, wherein the alkoxylate is an ethoxylate.

51. The method according to claim 48, wherein the alkoxylate is butanol ethoxylate.

52. The method according to claim 48, wherein the alkoxylate is butoxytriglycol.

53. The method according to claim 48, wherein the phenolic derivative is an alkyl- or aryl-substituted phenol.

54. The method according to claim 48, wherein the sulfate is an alkyl sulfate.

55. The method according to claim 48, wherein the sulfonate is an alkylaryl sulfonate or an alkyl sulfonate.

56. The method according to claim 48, wherein the phosphate is tripolyphosphate.

57. The method according to claim 48, wherein the monomeric amide is acetamide.

58. The method according to claim 48, wherein the fatty acid amide is tall oil amide.

59. The method according to claim 48, wherein the quaternary ammonium compound is trimethylglycine or distearyldimethylammonium chloride.

60. The method according to claim 48, wherein the vegetable oil is castor oil, palm oil, linseed oil, tall oil, or soybean oil.

61. The method according to claim 1 or 30, wherein based on the dry weight of component i, the content of component iii in the aqueous binder and / or binder composition is from 0.5 wt% to 50 wt%.

62. The method according to claim 61, wherein based on the dry weight of component i, the content of component iii in the aqueous binder and / or binder composition is from 2.5 wt% to 25 wt%.

63. The method according to claim 61, wherein based on the dry weight of component i, the content of component iii in the aqueous binder and / or binder composition is from 3 wt% to 15 wt%.

64. The method according to claim 1 or 30, wherein the aqueous binder and / or binder composition comprises: Additional component iv in the form of one or more coupling agents.

65. The method according to claim 64, wherein the component iv is an organofunctional silane.

66. The method according to claim 1 or 30, wherein the aqueous binder and / or binder composition further comprises: Component v in the form of one or more components selected from ammonia, amines or any salts thereof.

67. The method according to claim 1 or 30, wherein the aqueous binder and / or binder composition comprises: Additional component in the form of urea.

68. The method according to claim 67, wherein the additional component is present in an amount of from 5 wt% to 40 wt% based on the dry weight of component i.

69. The method according to claim 67, wherein the additional component is present in an amount of from 10 wt% to 30 wt% based on the dry weight of component i.

70. The method according to claim 67, wherein the additional component is present in an amount of from 15 wt% to 25 wt% based on the dry weight of component i.

71. The method according to claim 1 or 30, wherein the aqueous binder and / or binder composition comprises: - Component i in the form of one or more oxidized lignins; - Component ii in the form of one or more crosslinking agents; - Component iii in the form of one or more plasticizers; - Component iv in the form of one or more coupling agents; - Water.

72. The method according to claim 71, wherein the component iv is an organofunctional silane.

73. The method according to claim 71, wherein the aqueous adhesive and / or binder composition further comprises the following components: in the form of one or more compounds selected from ammonia, amines or any salts thereof.

74. The method according to claim 71, wherein the aqueous adhesive and / or binder composition further comprises the following components: in the form of urea.

75. The method according to claim 71, wherein the aqueous adhesive and / or binder composition further comprises the following components: in the form of more reactive or non-reactive polysiloxanes.

76. The method according to claim 71, wherein the aqueous adhesive and / or binder composition further comprises the following components: in the form of hydrocarbon oil.

77. The method according to claim 71, wherein the aqueous adhesive and / or binder composition further comprises the following components: in the form of one or more surfactants.

78. An insulating product obtained by the method according to any one of claims 1 to 77.

79. An insulating product comprising an insulating element which is a bonded artificial vitreous fiber batt with an adhesive, wherein the artificial vitreous fiber batt comprises at least one major surface and comprises a facing, wherein the facing is fixed to at least one major surface of the insulating element by a crosslinked adhesive, wherein the adhesive before curing is an aqueous adhesive composition, and the aqueous adhesive composition comprises: - Component i in the form of one or more oxidized lignins; - Component ii in the form of one or more crosslinking agents; - Component iii in the form of one or more plasticizers.

80. The product according to claim 78 or 79, wherein component i is in the form of one or more ammonia lignins.

81. The product according to claim 78 or 79, wherein the component ii comprises one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

82. The product according to claim 78 or 79, wherein the component ii comprises: - One or more crosslinking agents selected from polyethyleneimine, polyvinylamine, fatty amines; and / or - One or more crosslinking agents in the form of fatty acid amides; and / or - One or more crosslinking agents selected from dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid; and / or -One or more crosslinking agents selected from polyester polyols; and / or - One or more crosslinking agents selected from starch, modified starch, CMC; and / or - One or more crosslinking agents in the form of aliphatic polyfunctional carbodiimides; and / or - One or more crosslinking agents selected from melamine-based crosslinking agents.

83. The article according to claim 82, wherein the polyester polyol is polycaprolactone.

84. The article according to claim 82, wherein the melamine crosslinking agent is a hexa(methyl methoxy) melamine crosslinking agent.

85. The article according to claim 78 or 79, wherein based on the dry weight of component i, the aqueous adhesive and / or binder composition comprises component ii in an amount of 1 wt% to 40 wt%.

86. The article according to claim 85, wherein based on the dry weight of component i, the aqueous adhesive and / or binder composition comprises component ii in an amount of 4 wt% to 20 wt%.

87. The article according to claim 85, wherein based on the dry weight of component i, the aqueous adhesive and / or binder composition comprises component ii in an amount of 6 wt% to 12 wt%.

88. The article according to claim 78 or 79, wherein component iii comprises one or more plasticizers selected from polyethylene glycol, polyethers, hydrogenated sugars, phthalates, acids, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, and / or lactides.

89. The article according to claim 88, wherein the acid is: adipic acid, vanillic acid, lactic acid, and / or ferulic acid.

90. The article according to claim 88, wherein the polyether is polyethylene glycol ether.

91. The article according to claim 88, wherein the acrylic polymer is an acrylic polymer having free carboxyl groups.

92. The article according to claim 88, wherein the polyurethane dispersion is a polyurethane dispersion having free carboxyl groups.

93. The article according to claim 78 or 79, wherein component iii comprises: - One or more plasticizers selected from fatty alcohols, monohydroxy alcohols; and / or - One or more plasticizers selected from alkoxylates; and / or - One or more plasticizers in the form of propylene glycol; and / or - One or more plasticizers in the form of ethylene glycol esters; and / or - One or more plasticizers selected from adipates, acetates, benzoates, cyclohexanecarboxylates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates; and / or - One or more plasticizers selected from phenolic derivatives; and / or - One or more plasticizers selected from silanols, siloxanes; and / or - One or more plasticizers selected from sulfates, sulfonates and / or - Phosphates; and / or - One or more plasticizers in the form of hydroxy acids; and / or - One or more plasticizers selected from monomeric amides, benzamides, fatty acid amides; and / or - One or more plasticizers selected from quaternary ammonium compounds; and / or - One or more plasticizers selected from vegetable oils; and / or - One or more plasticizers selected from hydrogenated oils, acetylated oils; and / or - One or more plasticizers selected from acidic methyl esters; and / or - One or more plasticizers selected from alkyl polyglycosides, glucamides, aminoglucamides, sucrose esters, sorbitol esters; and / or - One or more plasticizers selected from polyethylene glycol, polyethylene glycol ethers.

94. The article according to claim 93, wherein the monohydroxy alcohol is amyl alcohol or stearyl alcohol.

95. The article according to claim 93, wherein the alkoxylate is an ethoxylate.

96. The article according to claim 93, wherein the alkoxylate is butanol ethoxylate.

97. The article according to claim 93, wherein the alkoxylate is butoxytriglycol.

98. The article according to claim 93, wherein the phenolic derivative is an alkyl- or aryl-substituted phenol.

99. The article according to claim 93, wherein the sulfate is an alkyl sulfate.

100. The article according to claim 93, wherein the sulfonate is an alkylaryl sulfonate or an alkyl sulfonate.

101. The article according to claim 93, wherein the phosphate is tripolyphosphate.

102. The article according to claim 93, wherein the monomeric amide is acetamide.

103. The article according to claim 93, wherein the fatty acid amide is tall oil amide.

104. The article according to claim 93, wherein the quaternary ammonium compound is trimethylglycine or distearyldimethylammonium chloride.

105. The article according to claim 93, wherein the vegetable oil is castor oil, palm oil, linseed oil, tall oil, or soybean oil.

106. The article according to claim 78 or 79, wherein based on the dry weight of component i, the content of component iii in the aqueous adhesive and / or binder composition is 0.5 wt% to 50 wt%.

107. The article according to claim 106, wherein based on the dry weight of component i, the content of component iii in the aqueous adhesive and / or binder composition is 2.5 wt% to 25 wt%.

108. The article according to claim 106, wherein based on the dry weight of component i, the content of component iii in the aqueous adhesive and / or binder composition is 3 wt% to 15 wt%.

109. The article according to claim 78 or 79, wherein the aqueous adhesive and / or binder composition comprises: Additional component iv, which is in the form of one or more coupling agents.

110. The article according to claim 109, wherein component iv is an organofunctional silane.

111. The article according to claim 78 or 79, wherein the aqueous adhesive and / or binder composition further comprises: Component v, which is in the form of one or more components selected from ammonia, amines or any salts thereof.

112. The article according to claim 78 or 79, wherein the aqueous adhesive and / or binder composition comprises: Additional component, which is in the form of urea.

113. The article according to claim 112, wherein the additional component is in an amount of 5 wt% to 40 wt% based on the dry weight of component i.

114. The article according to claim 112, wherein the additional component is in an amount of 10 wt% to 30 wt% based on the dry weight of component i.

115. The article according to claim 112, wherein the additional component is in an amount of 15 wt% to 25 wt% based on the dry weight of component i.

116. The article according to claim 78 or 79, wherein the aqueous adhesive and / or binder composition comprises: - Component i, which is in the form of one or more oxidized lignins; - Component ii, which is in the form of one or more crosslinking agents; - Component iii, which is in the form of one or more plasticizers; - Component iv, which is in the form of one or more coupling agents; - Water.

117. The article according to claim 116, wherein component iv is an organofunctional silane.

118. The article according to claim 116, wherein the aqueous adhesive and / or binder composition further comprises the following components: It is in the form of one or more compounds selected from ammonia, amines or any salts thereof.

119. The article according to claim 116, wherein the aqueous adhesive and / or binder composition further comprises the following components: It is in the form of urea.

120. The article according to claim 116, wherein the aqueous adhesive and / or binder composition further comprises the following components: It is in the form of a more reactive or non-reactive polysiloxane.

121. The article according to claim 116, wherein the aqueous adhesive and / or binder composition further comprises the following components: It is a hydrocarbon oil.

122. The article according to claim 116, wherein the aqueous adhesive and / or binder composition further comprises the following components: It is one or more surfactants.

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