RU2778640C9 - Products of mineral wool - Google Patents

Abstract

FIELD: construction.

SUBSTANCE: product of mineral wool and its production method, which can be used in the construction and other industries, are proposed. The product contains mineral fibers fixed with a cured binder, wherein the binder in its uncured state contains: at least one protein, at least one enzyme, where at least one protein is selected from a group consisting of animal proteins, including collagen, gelatin, hydrolyzed gelatin, and milk proteins – casein, whey, eggs; vegetable proteins, including proteins from legumes, cereals, whole grains, nuts, seeds and fruits, such as protein from buckwheat, oats, rye, millet, maize – corn, rice, wheat, bulgur, sorghum, amaranth, quinoa, soybeans – soy protein, lentils, beans, white beans, mung, chickpeas, cow peas, lima beans, pigeon peas, lupine beans, square peas, almond, Brazil nut, cashew, pecan, walnut, cotton seed, pumpkin seed, hemp seed, sesame seed, and sunflower seed; polyolefin proteins, such as protein of mussel leg, and where at least one enzyme is selected from a group consisting of transglutaminase (EC 2.3.2.13), protein disulfide isomerase (EC 5.3.4.1), thiol oxidase (EC 1.8.3.2), polyphenol oxidase (EC 1.14.18.1), in particular catechol oxidase, tyrosine oxidase, and phenol oxidase, lysyl oxidase (EC 1.4.3.13), and peroxidase (EC 1.11.1.7). Losses on ignition (LOI) of the product of mineral wool are in the range of 0.1-25.0%. The method for the production of the specified product of mineral wool includes stages of introduction of mineral fibers into a contact with the specified binder and curing of the binder.

EFFECT: increase in ecological safety at a low temperature of curing of a binder, possibility of self-restoration of products of mineral wool, obtained using these binders.

13 cl, 3 tbl

Description

Scope of the invention

The present invention relates to a mineral wool product with a binder and to a method for producing a mineral wool product with a binder.

Prerequisites for the creation of the invention

Mineral fibers typically contain man-made vitreous fibers (MMVF), such as, for example, glass fibers, ceramic fibers, basalt fibers, slag wool, mineral wool and stone wool, which are bonded with a cured thermosetting polymer binder material. For use as thermal and acoustic insulation products, bonded mineral fiber mats are usually prepared by converting the melt obtained from suitable raw materials into fibers in a conventional manner, for example by spinning cup or cascaded rotary process. The fibers are blown into the forming chamber and, during the air transfer process and while still hot, are sprayed with a binder solution and randomly laid in the form of a mat or web on a moving conveyor. The fiber mat is then transferred to a curing oven where hot air is blown through the mat to cure the binder and firmly bond the mineral fibers together.

The previously preferred binder resins have been phenol-formaldehyde resins, which can be economically prepared and can be diluted with urea prior to use as a binder. However, existing and proposed legislation to reduce or eliminate formaldehyde emissions has led to the development of formaldehyde-free binders, such as, for example, binder compositions based on polycarboxylic polymers and polyols or polyamines, as described in EP-A-583086, EP-A-990727, EP-A-1741726, US-A-5,318,990 and US-A-2007/0173588.

Another group of non-phenol-formaldehyde binders are the products of coupling/elimination reactions of aliphatic and/or aromatic anhydrides with alkanolamines, as described in WO 99/36368, WO 01/05725, WO 01/96460, WO 02/06178, WO 2004/007615 and WO 2006/061249. These binder compositions are water soluble and have excellent bonding properties in terms of cure rate and cure density. WO 2008/023032 describes urea-modified binders of a type that makes it possible to obtain mineral wool products that exhibit reduced moisture absorption.

Since some of the raw materials used in the manufacture of such binders are quite expensive chemicals, there remains a need for formaldehyde-free binders that can be produced economically.

An additional effect related to previously known aqueous mineral fiber binder compositions is that at least most of the raw materials used to manufacture these binders are derived from fossil fuels. Consumers currently tend to prefer products that are wholly or at least partially made from renewable materials, and hence there is a need to provide mineral wool binders that are at least partially made from renewable materials.

An additional effect related to previously known aqueous mineral fiber binder compositions is that they contain components that are corrosive and/or harmful. In this case, it is necessary to take measures to protect the equipment associated with the production of mineral wool products in order to avoid corrosion, and also to the persons working with this equipment, it is necessary to observe safety measures. This leads to increased costs and health problems, and hence there is a need to provide mineral fiber binder compositions with reduced levels of corrosive and/or harmful materials.

Another effect related to previously known aqueous mineral fiber binder compositions is that the manufacture of these binders typically requires significant binder curing equipment. The curing equipment is typically an oven operating at temperatures well above 100°C, eg around 200°C. The oven has a length of several meters, which ensures operation with a web continuously fed into it and the fact that the web leaving the oven is fully cured. Such furnace equipment is characterized by a very high energy consumption.

EP 2424886 B1 (Dynea OY) describes a composite material containing a cross-linkable resin of a proteinaceous material. In a typical embodiment, the composite material is a casting containing an inorganic filler, such as sand and/or wood, and a proteinaceous material, as well as enzymes capable of crosslinking the proteinaceous material. EP 2424886 B1 does not describe a mineral wool product.

Statement of the Invention

Accordingly, it has been an object of the present invention to provide a mineral wool product comprising mineral fibers bonded with a cured binder, wherein the binder uses renewable materials as raw materials and reduces or eliminates the use of corrosive and/or hazardous materials.

It was further an object of the present invention to provide a mineral wool product containing mineral fibers held together with a cured binder that does not require high temperature curing during product preparation.

A further object of the present invention was to provide a process for producing such a mineral wool product.

According to a first aspect of the present invention, there is provided a mineral wool product comprising mineral fibers held together by a cured binder, the binder in its uncured state comprising:

- at least one protein,

- at least one enzyme.

According to a second aspect of the present invention, there is provided a process for producing a mineral wool product, comprising the steps of contacting mineral fibers with such a binder composition.

The inventors of the present invention have surprisingly found that it is possible to obtain a mineral wool product containing mineral fibers bonded with a cured binder, wherein the binder composition can be obtained for the most part from renewable materials, the composition does not contain or only to a small extent contains any corrosive and / or harmful agents, and the manufacture of the mineral wool product does not result in emissions, such as emissions of VOCs (Volatile Organic Compounds), during the manufacturing process.

Description of Preferred Embodiments

The mineral wool product of the present invention comprises mineral fibers held together by a cured binder, the binder in its uncured state comprising:

- at least one protein,

- at least one enzyme.

In one embodiment, the mineral wool product binder is a formaldehyde-free binder.

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

An unexpected advantage of the embodiments of mineral wool products in accordance with the present invention is that they have self-healing properties. After exposure to very harsh conditions, where mineral wool products lose some of their strength, mineral wool products in accordance with the present invention can partially regain their original strength. This is in contrast to traditional mineral wool products where the loss of strength after exposure to harsh environments is irreversible. Without being bound by any particular theory, the present inventors believe that this unexpected property of the mineral wool products of the present invention is due to the complex nature of the bonds forming the network of enzyme-crosslinked proteins, also containing quaternary structures and hydrogen bonds, which ensures the formation of links in the network after returning to normal environmental conditions. In the case of an insulating product, which, when used, for example as roof insulation, can be exposed to very high temperatures in summer, this is an important advantage for ensuring the long-term stability of the product.

In one embodiment, the rock wool product is a rock wool insulating product, such as a rock wool product for thermal or acoustic insulation.

In one embodiment, the mineral wool product is a horticultural soil substrate.

Protein component of the binder

Preferably, the protein component of the binder is in the form of one or proteins selected from the group consisting of proteins of animal origin, including collagen, gelatin, hydrolyzed gelatin, and proteins from milk (casein, whey), eggs; plant-based proteins, including proteins from legumes, cereals, whole grains, nuts, seeds, and fruits such as protein from buckwheat, oats, rye, millet, maize (corn), rice, wheat, bulgur, sorghum, amaranth, quinoa, soy beans (soy protein), lentils, kidney beans, white beans, mung beans, chickpeas, cowpeas, lima beans, pigeon peas, lupine beans, square peas, almonds, Brazil nuts, cashews, pecans, walnuts, cottonseed, pumpkin seeds, hemp seed, sesame seed and sunflower seed; polyphenolic proteins such as mussel leg protein.

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

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

In a preferred embodiment, the protein component is gelatin, wherein the gelatin is preferably derived from one or more sources from the group consisting of mammalian and avian species such as cow, pig, horse, poultry, and/or fish scale, skin.

In one embodiment, the gelatin is high strength gelatin.

In one embodiment, the protein contains polyphenolic proteins. These proteins contain high levels of the post-translationally modified-oxidized form of tyrosine, L-3,4-dihydroxyphenylalanine (levodopa, L-DOPA). See also J. J. Wilker Nature Chem. Biol. 2011, 7, 579–580 for information on these proteins.

Enzymatic binder component

In a preferred embodiment, the binder enzyme component is selected from the group consisting of transglutaminase (EC 2.3.2.13), protein disulfide isomerase (EC 5.3.4.1), thiol oxidase (EC 1.8.3.2), polyphenol oxidase (EC 1.14.18.1), in particular catechol oxidase, tyrosine oxidase and phenol oxidase, lysyl oxidase (EC 1.4.3.13) and peroxidase (EC 1.11.1.7).

Enzymes can be of both natural origin and recombinant origin.

In a specific preferred embodiment, the protein component is gelatin, in particular pigskin gelatin, in particular medium gel strength, and the enzyme component is transglutaminase (EC 2.3.2.13).

Reaction of binder components

The present inventors have found that, in some embodiments, the mineral wool product of the present invention is best obtained when the binder is applied to the mineral fibers under acidic conditions. Thus, in a preferred embodiment, the binder applied to the mineral fibers contains a pH adjuster, in particular in the form of a pH buffer.

In a preferred embodiment, the uncured binder has a pH less than 8, such as less than 7, such as less than 6.

The components may be other additives, such as one or more reactive or non-reactive silicones, which can be added to the binder. Preferably, the one or more reactive or non-reactive silicones are selected from the group consisting of a silicone consisting of a backbone that contains silicone moieties, especially diphenylsiloxane moieties, alkylsiloxane moieties, preferably dimethylsiloxane moieties, bearing at least one hydroxyl, acyl, carboxyl or anhydride, an amine, epoxy or vinyl functional group capable of reacting with at least one of the components of the binder composition, preferably present in an amount of 0.1-15 wt.%, preferably 0.1-10 wt.%, more preferably 0, 3–8 wt.%, from the total mass of the binder.

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

In one embodiment, an anti-fouling agent may be added to the binder composition.

In one embodiment, at least one antifouling agent is a tannin, in particular a tannin selected from one or more components of the group consisting of tannic acid, condensed tannins (proanthocyanidins), hydrolyzable tannins, gallotannins, ellagitannins, complex tannins and/or tannin obtained from one or more of oak, chestnut, staghorn sumac and tellima grandiflora.

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

Additional supplements may include supplements containing calcium ions (which stabilizes the transglutaminase enzyme) and antioxidants.

In one embodiment, the binder composition according to the present invention contains additives in the form of crosslinkers containing acyl groups and/or amino groups and/or thiol groups. These crosslinkers can reinforce and/or modify the polymer network of the cured binder.

In one embodiment, the binder compositions of the present invention contain further additives in the form of additives selected from the group consisting of PEG-like reagents, silanes, or hydroxylapatites.

Product properties of mineral wool

In a preferred embodiment, the density of the mineral wool product is in the range of 10-900 kg/m ³ , eg 30-800 kg/m ³ , eg 40-600 kg/m ³ , eg 50-250 kg/m ³ , eg 60- 200 kg/m ³ .

In a preferred embodiment, the mineral wool product according to the present invention is an insulating product, in particular having a density of 10-200 kg/m ³ .

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

Method for obtaining a product from mineral wool

The present invention also provides a process for producing a mineral wool product by bonding mineral fibers with a binder composition.

A particular advantage of the mineral wool product according to the present invention is that it does not require high temperatures to cure. This not only saves energy, reduces VOC emissions, and reduces the need for equipment to withstand high temperatures, but also allows high flexibility in the production of mineral wool products using these binders.

In one embodiment, the method includes the following steps:

- obtaining a melt of raw materials,

- forming fibers from the melt using a fiber forming apparatus to obtain mineral fibers,

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

mixing the binder with the mineral fibers before, during or after the fabric is assembled to provide a mixture of the mineral fibers and the binder,

- curing the mixture of mineral fibers and binder.

In one embodiment, the binder is fed in close proximity to the fiber-forming apparatus, for example a centrifugal spinning apparatus or a cascade spinning apparatus, in any case immediately after the formation of fibers. The binder-coated fibers are then transported on a conveyor belt in the form of a web.

The web may be subjected to longitudinal compression after fiber formation and prior to substantial curing.

Fiber forming apparatus

There are different types of centrifugal spinning machines for spinning fibers from mineral melts.

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

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

Many fibre-forming apparatuses comprise a disk or cup rotating about a substantially vertical axis. It is traditional to arrange several such spinning devices in a line, i.e. essentially in the first direction, for example as described in GB-A-926,749, US-A-3,824,086 and WO-A-83/03092.

Typically, an airflow is used associated with one or each of the fiber forming rotors, and the fibers are entrained by this airflow as they are formed from the surface of the rotor.

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

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

As used herein, the term "collected web" shall include all mineral fibers collected together at the surface, i.e. no longer entrained in air, for example formed mineral fibres, granules, bundles or recycled web scraps. The collected fiber may be a virgin web formed by collecting the fibers on a conveyor belt and provided as starting material without batting or other consolidation.

Alternatively, the collected web may be a secondary web formed by batting or otherwise consolidating the primary web. Preferably the assembled web is a virgin web.

In one embodiment, the mixing of the binder with the mineral fibers is done after providing the assembled web, using the following steps:

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

- suspension of mineral fibers in the primary air flow,

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

A process for producing a mineral wool product, including a disentangling process step, is described in EP10190521.

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

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

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

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

It is also acceptable to pre-mix the binder with the collected mineral fiber web prior to the untangling process. Additional mixing can be carried out during the disentangling process and after it. In an alternative embodiment, the binder may be introduced into the primary air stream separately and mixed into the primary air stream.

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

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

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

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

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

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

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

curing

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

In one embodiment, curing occurs in a curing device.

In one embodiment, curing is carried out at temperatures of 5-95°C, eg 5-80°C, eg 5-60°C, eg 8-50°C, eg 10-40°C.

In one embodiment, curing takes place in a conventional mineral wool curing oven that operates at temperatures of 5-95°C, eg 5-80°C, eg 10-60°C, eg 20-40°C.

The curing process can begin immediately after the binder has been applied to the fibres. Curing is defined as the process by which a chemical reaction occurs in a binder composition that typically increases the molecular weight of the compounds in the binder composition and thereby increases the viscosity of the binder composition, typically until the binder composition reaches a solid state.

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

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

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

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

The curing of the binder in contact with the mineral fibers in a heat press has a particular advantage in that high density products can be obtained.

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

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

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

In one embodiment, curing is performed in an oxygen depleted environment.

Without being limited by any particular theory, the applicant believes that performing curing in an oxygen depleted environment increases the stability of the enzyme component in some embodiments, especially the transglutaminase enzyme, and thereby improves crosslinking efficiency. In one embodiment, the curing process is thus carried out in an inert atmosphere, in particular an atmosphere of an inert gas such as nitrogen.

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

Advantages of the binder composition

The mineral wool product according to the present invention has the unexpected advantage that it can be made using a very simple binder requiring only two components, namely at least one protein and at least one enzyme, for This binder does not require any pre-reaction. Thus, the mineral wool product according to the present invention is made from natural and non-toxic ingredients and is therefore safe to handle. At the same time, the mineral wool product of the present invention is produced using a binder based on renewable resources.

Because the binder used to manufacture the mineral wool product of the present invention can be cured at ambient or near ambient temperature, the energy consumption for manufacturing such products is very low. The non-toxic and non-corrosive nature of the binder embodiments, combined with ambient temperature curing, can significantly reduce the use of complex equipment. At the same time, given that the curing takes place at ambient temperature, the likelihood of spots of uncured binder is significantly reduced.

Additional important advantages are the self-healing capabilities of mineral wool products produced using these binders.

Another advantage of mineral wool products is that they can be shaped to the desired shape after application of the binder but before curing. This provides an opportunity for the production of specialized products such as pipe sections.

Another benefit is the significantly reduced risk of burnout.

Burnout can be associated with exothermic reactions during the manufacture of a mineral wool product that increase temperatures within the core of the insulating material, causing the mineral fibers to fuse or devitrify, and ultimately create a fire hazard. In the worst case, burnout can cause a fire in stacks of boards in warehouses or during transportation.

Another advantage is the absence of curing emissions, in particular the absence of emissions of volatile organic compounds.

Examples

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

Prior Art Binders

For prior art binders, the following properties were determined.

Reagents

50% aq. hypophosphorous acid solution and 28% aq. ammonia solution was supplied by Sigma Aldrich. D-(+)-glucose monohydrate was supplied by Merck. 75.1% aq. glucose syrup with a DE value of 95 to less than 100 (C*sweet D 02767 ex Cargill) was supplied by Cargill. The silane (Momentive VS-142) was provided by Momentive and was considered 100% for simplicity. All other high purity components were supplied by Sigma-Aldrich and were considered anhydrous for simplicity.

Solids content of binder components, determination

The content of each of the components in a given binder solution prior to curing was calculated from the dry weight of the components. You can use the following formula:

Binder solids, definition and procedure

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

Disc-shaped stone wool samples (diameter: 5 cm; height 1 cm) were cut from the stone wool and heat-treated at 580° C. for at least 30 minutes to remove all organic matter. The solids content of the binder mixture (see below for examples of mixtures) was measured by spreading a sample of the binder mixture (about 2 g) over a heat-treated stone wool disk in a foil container. The weight of the foil container containing the stone wool disc was determined before and immediately after the addition of the binder mixture. Provided two such stone wool disks coated with a binder mixture in foil containers and heated them at 200°C for 1 hour.

After cooling and keeping at room temperature for 10 minutes, the samples were weighed and the amounts of binder solids were determined as the average of the two results. Thereafter, a binder with the desired binder solids content could be obtained by dilution using the required amount of water and 10% aq. silane solution (Momentive VS-142).

Reaction loss, definition

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

Mechanical strength studies (tablet tests), procedure

The mechanical strength of the binders was investigated in a tablet test. For each binder, six tablets were made from a mixture of binder and stone wool granules formed in the stone wool spinning process. The pellets are particles having the same melt composition as the stone wool fibers and the pellets are generally considered to be spinning waste. The granules used in the formulation of tablets are 0.25–0.50 mm in size.

A binder solution with 15% binder solids containing 0.5% silane (Momentive VS-142) from binder solids was prepared as described above in the binder solids section. A sample of this binder solution (4.0 g) was mixed well with the granules (20.0 g). The resulting mixture was then transferred to a round aluminum foil container (bottom Ø = 4.5 cm, top Ø = 7.5 cm, height = 1.5 cm). The mixture was then strongly compressed using a flat-bottomed beaker or a suitably sized plastic beaker to obtain a flat tablet surface. Six tablets were thus obtained from each binder. The resulting tablets were further cured at 250° C. for 1 hour. After cooling to room temperature, the tablets were carefully removed from the containers. Three tablets were aged in a water bath at 80°C for 3 hours.

After drying for 1-2 days, all tablets were broken in a 3-point bend test (test speed: 10.0 mm/min; break rate: 50%; nominal force: 30 MPa (30 N/mm ² ); distance: 40 mm, max deflection 20 mm, nominal modulus of elasticity 10,000 MPa (10,000 N/mm ² )) on a Bent Tram to test their mechanical strength. The tablets were placed in the device with the "bottom surface" up (ie the surface with Ø = 4.5 cm).

Theoretical binder content in tablets, determination

The theoretical binder content of tablets is calculated by dividing the amount of binder solids used to make the tablet by the sum of the binder solids and granules used to make the tablet. You can use the following formula:

Six tablets were prepared for each binder mixture. The theoretical binder content for each test was calculated as the average of these six tablets.

Comparative Examples - Prior Art Reference Binders

Binder Example, Reference Binder A

A mixture of anhydrous citric acid (10.2 g, 53.1 mmol) and D-(+)-glucose monohydrate (57.3 g; thus in fact 52.1 g dextrose) in water (157.5 g) was stirred at room temperature until a clear solution is obtained. Then added dropwise 28% aq. ammonia solution (7.80 g; thus actually 2.16 g, 128.4 mmol ammonia). Next, the amount of binder solids was measured (17.4%). For mechanical strength tests (15% binder solids solution containing 0.5% silane from binder solids), the binder mixture was diluted with water (0.149 g/g binder mixture) and 10% aq. silane solution (0.009 g/g binder mixture, Momentive VS-142). The finished binder mixture had a pH of 5.1.

Binder Example, Reference Binder B (urea-modified phenol-formaldehyde resin, PUF-resol)

Phenol-formaldehyde resin was obtained by the reaction of 37% aq. a solution of formaldehyde (606 g) and phenol (189 g) in the presence of 46% aq. potassium hydroxide solution (25.5 g) at a reaction temperature of 84°C, preceded by heating at a rate of about 1°C per minute. The reaction was continued at 84° C. until the acid resistance of the resin reached 4 and most of the phenol was consumed. Next, urea (241 g) was added and the mixture was cooled.

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

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

AT = (Volume of Titration Solution Used (mL)) / (Volume of Sample (mL))

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

Binder Example, Reference Binder C

A mixture of L-ascorbic acid (1.50 g, 8.52 mmol) and 75.1% aq. glucose syrup (18.0 g; thus, effectively 13.5 g glucose syrup) in water (30.5 g) was stirred at room temperature until a clear solution was obtained. Then 50% aq. hypophosphorous acid solution (0.60 g; thus in fact 0.30 g, 4.55 mmol hypophosphorous acid) and urea (0.75 g). Then, until pH = 6.9 was reached, 28% aq. ammonia solution (0.99 g; thus actually 0.28 g, 16.3 mmol ammonia). Next, the solids content of the binder was measured (21.5%). For mechanical strength tests (15% binder solids solution containing 0.5% silane from binder solids), the binder mixture was diluted with water (0.423 g/g binder mixture) and 10% aq. silane solution (0.011 g/g binder mixture, Momentive VS-142). The finished binder mixture had a pH of 7.0.

Binder Example, Reference Binder D

A mixture of 75.1% aq. glucose syrup (60.0 g; thus, effectively 45.0 g glucose syrup), ammonium sulfamate (2.25 g, 19.7 mmol) and urea (2.25 g) in water (105.1 g) were stirred at room temperature until a clear solution is obtained. Then, until pH = 8.2 was reached, 28% aq. ammonia solution (0.12 g; thus effectively 0.03 g, 1.97 mmol ammonia). Next, the amount of binder solids was measured (21.6%). For mechanical strength tests (15% binder solids solution containing 0.5% silane from binder solids), the binder mixture was diluted with water (0.432 g/g binder mixture) and 10% aq. silane solution (0.011 g/g binder mixture, Momentive VS-142). The finished binder mixture had a pH of 8.2.

Binder Example, Reference Binder E (based on reaction products of alkanolamine-polycarboxylic acid anhydride)

Diethanolamine (DEA, 231.4 g) was placed in a 5 liter glass reactor equipped with a stirrer and a heating/cooling jacket. The temperature of diethanolamine was raised to 60° C. whereupon tetrahydrophthalic anhydride (THFA, 128.9 g) was added. After raising the temperature to 130° C. and maintaining it at this level, a second portion of tetrahydrophthalic anhydride (64.5 g) was added, followed by trimellitic anhydride (TMA, 128.9 g). After maintaining the temperature at 130°C for 1 hour, the mixture was cooled to 95°C. Water (190.8 g) was added and stirring was continued for 1 hour. After cooling to ambient temperature, the mixture was poured into water (3.40 kg) and 50% aq. hypophosphorous acid solution (9.6 g) and 25% aq. ammonia solution (107.9 g). Glucose syrup (1.11 kg) was heated to 60°C and then added with stirring, after which was added 50% aq. silane solution (5.0 g, Momentive VS-142). The binder solids content was then measured as described above, after which the mixture was diluted with the required amount of water for mechanical strength measurements (15% binder solids solutions).

Binder Example, Reference Binder F (based on reaction products of alkanolamine-polycarboxylic acid anhydride)

Diethanolamine (DEA, 120.5 g) was placed in a 5 liter glass reactor equipped with a stirrer and a heating/cooling jacket. The temperature of diethanolamine was raised to 60°C, after which tetrahydrophthalic anhydride (THFA, 67.1 g) was added. After raising the temperature to 130° C. and maintaining it at this level, a second portion of tetrahydrophthalic anhydride (33.6 g) was added, followed by trimellitic anhydride (TMA, 67.1 g). After maintaining the temperature at 130°C for 1 hour, the mixture was cooled to 95°C. Water (241.7 g) was added and stirring was continued for 1 hour. Urea (216.1 g) was then added and stirring continued until all solids were dissolved. After cooling to ambient temperature, the mixture was poured into water (3.32 kg) and 50% aq. hypophosphorous acid solution (5.0 g) and 25% aq. ammonia solution (56.3 g). Glucose syrup (1.24 kg) was heated to 60°C and then added with stirring, after which was added 50% aq. silane solution (5.0 g, Momentive VS-142). The binder solids content was then measured as described above, after which the mixture was diluted with the required amount of water for mechanical strength measurements (15% binder solids solutions).

Binders in accordance with the present invention

For the binders of the present invention, the following properties were determined.

Reagents

Pigskin gelatin with medium gel strength (170-195 g Bloom) and sodium hydroxide were obtained from Sigma-Aldrich. Transglutaminase TI was obtained from Modernist Pantry. For simplicity, these reagents were assumed to be completely pure and anhydrous.

Solids content of binder components, determination

The content of each of the components in a given binder solution prior to curing was calculated from the dry weight of the components. You can use the following formula:

The examples of binders below were mixed for convenience to a solids content of the binder components of 15 ± 1.5%.

Mechanical strength studies (tablet tests), procedure

The mechanical strength of the binders was investigated in a tablet test. For each binder, six tablets were made from a mixture of binder and stone wool granules formed in the stone wool spinning process. The pellets are particles having the same melt composition as the stone wool fibers and the pellets are generally considered to be spinning waste. The granules used in the formulation of tablets are 0.25–0.50 mm in size.

A binder mixture containing 15 ± 1.5% solids of the binder components was prepared as described in the examples below. A sample of this binder solution (4.0 g) was mixed well with the granules (20.0 g). The resulting mixture was then transferred to a round aluminum foil container (bottom Ø = 4.5 cm, top Ø = 7.5 cm, height = 1.5 cm). The mixture was evenly distributed in the container with a wide spatula, obtaining a flat tablet surface. Six tablets were thus obtained from each binder.

Containers with tablets made from binders designed to cure at room temperature were left at room temperature for two days. Tablet containers intended to cure below room temperature were first left at 11°C for one day and then for two days at room temperature. Containers with tablets intended to cure above room temperature were left at 41°C, 61°C, or 81°C for 5 hours, 2 hours, or 1 hour, respectively, and then for one day at room temperature.

The tablets were then carefully removed from the containers. Three tablets were aged in a water bath at 80°C for 3 hours.

After drying for two days, all tablets were broken in a 3-point bend test (test speed: 10.0 mm/min; break rate: 50%; nominal force: 30 MPa (30 N/mm ² ); reference distance: 40 mm, max deflection 20 mm, nominal modulus of elasticity 10,000 MPa (10,000 N/mm ² )) on Bent Tram to test their mechanical strength. The tablets were placed in the device with the "bottom surface" up (ie the surface with Ø = 4.5 cm).

Theoretical binder content in tablets, determination

The theoretical binder content of tablets is calculated by dividing the solids content of the binder component used in tablet preparation by the sum of the solids content of the binder component and the granules used in tablet preparation. You can use the following formula:

Six tablets were prepared for each binder mixture. The theoretical binder content for each test was calculated as the average of these six tablets.

Measured binder content in tablets, determination

The measured binder content of tablets is calculated by dividing the weight of the dried tablet minus the granules in the tablet by the weight of the dried tablet. You can use the following calculation:

Six tablets were prepared for each binder mixture. The measured binder content for each binder tested was calculated as the average of these six tablets.

Film tests, procedure

A binder mixture containing 15 ± 1.5% solids of the binder components was prepared as described in the examples below. A sample large enough to cover the bottom with a layer about 1–2 mm thick was then transferred to a round aluminum foil container (bottom Ø = 4.5 cm, top Ø = 7.5 cm, height = 1.5 cm) . For each binder mixture, two samples were obtained, which were then left at room temperature for two days.

The resulting films were carefully removed from the containers and one of the films was tested for water resistance by immersing the film halfway in water at a temperature of 80°C. In this test, the non-water resistant binder compositions had to dissolve rapidly.

Binder compositions according to the present invention

Binder example, point 1

Pigskin gelatin with medium gel strength (10.0 g) was allowed to swell in water (56.7 g) for 30 minutes at room temperature. The mixture was then placed in a water bath at 50° C. and stirred for several minutes until a clear solution (pH 5.1) was obtained. Before using in further experiments, the solution was stirred for another 30 minutes at 50°C.

Binder example, item 5

Pigskin gelatin with medium gel strength (10.0 g) was allowed to swell in water (56.7 g) for 30 minutes at room temperature. The mixture was then placed in a water bath at 50° C. and stirred for several minutes until a clear solution (pH 5.1) was obtained. Then 1 M NaOH (3.10 g) (pH 8.8) was added and the resulting mixture was stirred for another 30 minutes at 50° C. before being used in further experiments.

Binder example, point 6

Pigskin gelatin with medium gel strength (10.0 g) was allowed to swell in water (51.7 g) for 30 minutes at room temperature. The mixture was then placed in a water bath at 50° C. and stirred for several minutes until a clear solution (pH 5.2) was obtained. The solution was stirred for 30 minutes at 50° C. and then a solution of transglutaminase TI (0.20 g) in water (5.0 g) (pH 5.2) was added. Before using in further experiments, the resulting mixture was stirred for a few more minutes at 50°C.

Binder example, item 7

Pigskin gelatin with medium gel strength (10.0 g) was allowed to swell in water (51.7 g) for 30 minutes at room temperature. The mixture was then placed in a water bath at 50° C. and stirred for several minutes until a clear solution (pH 5.1) was obtained. The solution was stirred for 30 minutes at 50° C. and then a solution of transglutaminase TI (0.50 g) in water (5.0 g) (pH 5.2) was added. Before using in further experiments, the resulting mixture was stirred for a few more minutes at 50°C.

Binder example, item 8

Pigskin gelatin with medium gel strength (10.0 g) was allowed to swell in water (51.7 g) for 30 minutes at room temperature. The mixture was then placed in a water bath at 50° C. and stirred for several minutes until a clear solution (pH 5.3) was obtained. The solution was stirred for 30 minutes at 50° C. and then a solution of transglutaminase TI (1.00 g) in water (5.0 g) (pH 5.3) was added. Before using in further experiments, the resulting mixture was stirred for a few more minutes at 50°C.

The rest of the binders listed in Table 1 were prepared in a manner similar to the preparation methods described above.

Table 1-1

Reference binders Example A B C D E F Binder Composition Acid or ascorbic. acid (wt%) L-ascorbic acid - - ten - - - Lemon acid 16 - - - - - Carbohydrate (wt%) glucose syrup - 90 100 - - Glucose 84 - - - - - Additive (wt%) ^[a] hypophosphorous acid - - 2 - - - ammonium sulfamate - - - 5 - - Urea - - 5 5 - - Amine (equiv.) ^[b] Ammonia (added) 0.8 - 1.2 0.1 - - Silane (% binder solids) 0.5 0.5 0.5 0.5 - - Binder Properties Solids content of binder components (%) - - 21.8 20.2 21.1 21.6 Reaction Loss (%) 37.3 28.5 31.1 25.9 28.9 30.6 Binder solids (%) 15.0 15.0 15.0 15.0 15.0 15.0 pH of the binder mixture 5.1 9.6 7.0 8.2 6.1 6.2 Curing conditions Temperature (°C) 250 250 250 250 250 250 Tablet properties Theoretical binder content in tablets (%) ^[c] 2.9 2.9 2.9 2.9 2.9 2.9 Mechanical strength, without aging (kN) 0.17 0.16 0.16 0.16 0.20 0.09 Mechanical strength, with aging (kN) 0.13 0.09 0.08 0.09 0.16 0.07

^[a] Carbohydrate + ascorbic acid. ^[b] Amine molar equivalents relative to inorganic or organic acid molar equivalents. ^[c] Binder solids.

Table 1-2

Gelatin, various conditions (without transglutaminase) Example one 2 3 four 5 Binder Composition Protein (wt%) Gelatin (pigskin), medium gel strength 100 100 100 100 100 Enzyme Blend (wt%) ^[a] Transglutaminase TI - - - - - Base (wt%) ^[b] Sodium hydroxide - - - - 1.2 Binder Properties Solids content of binder components (%) 15.0 15.0 15.0 15.0 14.5 pH of the binder mixture 5.1 5.0 5.1 5.0 8.8 Curing conditions Temperature (°C) room pace. 43 61 81 room pace. Tablet properties Theoretical binder content in tablets (%) ^[c] 2.9 2.9 2.9 2.9 2.8 Measured binder content in tablets (%) 3.9 4.1 4.0 3.9 3.8 Mechanical strength, without aging (kN) 0.24 0.29 0.28 0.29 0.23 Mechanical strength, with aging (kN) 0 ^[d] 0 ^[d] 0 ^[d] 0 ^[d] 0 ^[d] Film Properties Durability in the aging test Not - - - Not

^[a] Gelatin. ^[b] Gelatin + transglutaminase. ^[c] Based on the solids content of the binder components. ^[d] In the process of aging, the complete destruction of the tablets was observed.

Table 1-3

Gelatin, transglutaminase, room pace. Gelatin, transglutaminase, different temp. Example 6 7 eight 9 ten eleven Binder Composition Protein (wt%) Gelatin (pigskin), medium gel strength 100 100 100 100 100 100 Enzyme Blend (wt%) ^[a] Transglutaminase TI 2 5 ten 5 5 5 Base (wt%) ^[b] Sodium hydroxide - - - - - - Binder properties Solids content of binder components (%) 15.3 15.6 16.3 15.6 15.6 15.6 pH of the binder mixture 5.2 5.2 5.3 5.0 5.1 5.1 Curing conditions Temperature (°C) room pace. room pace. room pace. eleven 43 61 Tablet properties Theoretical binder content in tablets (%) ^[c] 3.0 3.0 3.1 3.0 3.0 3.0 Measured binder content in tablets (%) 4.1 4.1 4.4 4.1 4.0 4.0 Mechanical strength, without aging (kN) 0.28 0.31 0.26 0.32 0.26 0.23 Mechanical strength, with aging (kN) 0.10 0.22 0.22 0.19 0.18 0.12 Film properties Durability in the aging test - Yes - - - -

^[a] Gelatin. ^[b] Gelatin + transglutaminase. ^[c] Based on the solids content of the binder components.

Based on the experimental results documented in Tables 1-1-1-3, the following observations and conclusions can be drawn.

When comparing the theoretical binder content and the measured binder content for the examples according to the present invention in Table 1-3, it can be seen that the measured binder content is significantly higher. The Applicant believes that this is partly the result of the incorporation of significant amounts of water of crystallization into the cured binder. In addition, due to curing at very low temperatures, the binders of the present invention do not experience any significant reactive losses. The corresponding higher LOI, i.e. higher binder content can be achieved using less organic starting material compared to other binders based on renewable resources such as reference binders A, C and D.

As can be seen from a comparison of the results shown in Table 1-3 with the results shown in Table 1-1, mineral wool products according to the present invention can have higher mechanical strength (aged and unaged) when using the same the amount of organic starting material for the binder (the theoretical state of the binder) and a much lower curing temperature. This allows you to provide an improved product while reducing energy consumption and using simpler equipment.

Claims (26)

1. A mineral wool product containing mineral fibers held together by a cured binder, the binder in its uncured state comprising: - at least one protein, - at least one enzyme, where at least one protein is selected from the group consisting of proteins of animal origin, including collagen, gelatin, hydrolyzed gelatin, and proteins from milk - casein, whey, eggs; plant-based proteins, including proteins from legumes, cereals, whole grains, nuts, seeds, and fruits such as protein from buckwheat, oats, rye, millet, maize - corn, rice, wheat, bulgur, sorghum, amaranth, quinoa, soybeans - soy protein, lentils, kidney beans, white beans, mung beans, chickpeas, cowpeas, lima beans, pigeon peas, lupine beans, square peas, almonds, Brazil nuts, cashews, pecans, walnuts, cottonseed, pumpkin seeds, hemp seeds , sesame seed and sunflower seed; polyphenolic proteins such as mussel leg protein, and where at least one enzyme is selected from the group consisting of transglutaminase (EC 2.3.2.13), protein disulfide isomerase (EC 5.3.4.1), thiol oxidase (EC 1.8.3.2), polyphenol oxidase (EC 1.14.18.1), in particular catechol oxidase, tyrosine oxidase and phenol oxidase, lysyl oxidase (EC 1.4.3.13) and peroxidase (EC 1.11.1.7), with the loss on ignition (LOI) of the mineral wool product being in the range of 0.1-25.0%. 2. The rock wool product of claim 1 wherein the collagen or gelatin is derived from one or more sources from the group consisting of mammalian and avian species such as cow, pig, horse, poultry, and/or scale, skin fish. 3. A mineral wool product according to any one of the preceding claims, wherein the binder in its uncured state contains a pH adjuster, in particular in the form of a pH buffer. 4. A mineral wool product according to any one of the preceding claims, wherein the binder in its uncured state has a pH of less than 8, such as less than 7, such as less than 6. 5. A mineral wool product according to any one of the preceding claims, wherein the binder contains at least one additive selected from the group consisting of crosslinkers containing acyl groups and/or amino groups and/or thiol groups. 6. A mineral wool product according to any one of the preceding claims, wherein the density of the mineral wool product is in the range of 10-900 kg/m ³ , for example 30-800 kg/m ³ , for example 40-600 kg/m ³ , for example 50 -250 kg / m ³ , for example 60-200 kg / m ³ . 7. A mineral wool product according to any one of the preceding claims, wherein the loss on ignition (LOI) is in the range of 0.3-18.0%, such as 0.5-12.0%, such as 0.7-8.0 wt %. 8. A process for producing a mineral wool product characterized by a loss on ignition (LOI) in the range of 0.1-25.0%, which includes the steps of bringing mineral fibers into contact with a binder in accordance with any of paragraphs. 1-7 and curing of the binder. 9. A method for producing a mineral wool product according to claim 8, including the following steps: - obtaining a melt of raw materials, - forming fibers from the melt using a fiber forming apparatus to obtain mineral fibers, - providing mineral fibers in the form of an assembled web, mixing the binder with the mineral fibers before, during or after the fabric is assembled to provide a mixture of the mineral fibers and the binder, - curing the mixture of mineral fibers and binder. 10. The method for producing a mineral wool product according to claim 9, wherein the mixing of the binder with mineral fibers is carried out after providing the assembled web, using the following steps: - exposing the collected mineral fiber web to the disentangling process, - suspension of mineral fibers in the primary air flow, - mixing the binder with mineral fibers before, during or after the disentanglement process to obtain a mixture of mineral fibers and binder. 11. The method of obtaining a product from mineral wool according to paragraphs. 8-10, in which curing is carried out at temperatures from 5 to 95°C, for example from 5 to 80°C, for example from 8 to 50°C, for example from 10 to 40°C. 12. The method of obtaining a product from mineral wool according to paragraphs. 8-11, wherein the curing process includes a drying process, in particular by blowing air or gas over the mineral wool product and/or by raising the temperature. 13. The method of obtaining a product from mineral wool according to paragraphs. 8-12, curing being carried out in an oxygen depleted environment.