RU2778791C2 - Product of mineral wool - Google Patents

Abstract

FIELD: material processing.

SUBSTANCE: invention relates to a method for the connection of surfaces of two or more elements to each other, wherein at least one of two or more elements is an element of mineral wool, as well as to a product of mineral wool manufactured by the specified method. The specified elements of mineral wool are bonded with a binder for mineral wool. The method for binding surfaces of two or more elements to each other includes following stages: provision of two or more elements; application of adhesive to one or more surfaces to be connected before, during or after bringing surfaces to be connected into contact with each other; curing of adhesive. Adhesive contains at least one protein and at least one phenol- and/or quinone-containing compound, and/or at least one enzyme. Moreover, the content of phenol- and/or quinone-containing compound in adhesive is from 1 to 70 wt. % of the dry weight of protein. At least one enzyme was 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).

EFFECT: reduction in exposure to hazardous substances during production, provision of a method for binding surfaces of two or more elements to each other, where at least one of two or more elements is an element of mineral wool.

20 cl, 1 dwg, 5 ex

Description

Scope of the invention

The present invention relates to a method for joining the surfaces of two or more elements to each other, wherein at least one of the two or more elements is a mineral wool element, as well as to a mineral wool product made by said method.

Prerequisites for the creation of the invention

The insulating performance of finished panels depends, among other things, on how the individual panels are installed and/or bonded to each other at the construction site. The more small panels are required to form the desired surface, the greater will be the number of sidewalls with which the panels will mutually adjoin. The greater the number of sidewalls with which the panels come into contact with each other, the more thermal bridges will form on the insulated surface as a result of inaccurate installation, improper alignment of individual panels, and also as a result of an increased risk of contamination of the contact surfaces.

Accordingly, there is a need for a method for joining the surfaces of two or more such mineral wool panels or other mineral wool elements to each other.

In addition, there is also a need for a method of bonding the surface of one or more rock wool elements to one or more non-rock wool elements.

In the past, phenol-formaldehyde resins, which are economical to manufacture, have been used as adhesive compositions to bond mineral wool elements together.

However, these adhesives have the disadvantage of containing formaldehyde, and therefore they are potentially hazardous to handle and require protective measures when handling on site.

Binders that are not phenol-formaldehyde and which can be used as adhesives are sugar-based binders, such as, for example, the compositions described in EP2990494A1, PCT/EP2015/080758, WO2007/014236, WO2011/138458 and WO2009/080938 .

However, all of these binders, when used as adhesives for bonding the surfaces of mineral wool elements to each other, will have the disadvantage that they require high temperatures for curing, which will result in the need to supply heat to the elements to be bonded to each other in over a long period of time. This work not only requires additional equipment, but can also be a fire hazard, for example when connecting together insulation elements for roof insulation on site. In addition, high temperature curing of these known adhesives may release harmful or irritating fumes, which may require the use of protective equipment when handling these materials.

Another type of adhesive that has been used to bond mineral wool elements to each other or to other elements such as fiberglass fleece or metal sheet is a polyurethane-based adhesive. It can be a one-component or two-component adhesive. Such adhesives do not necessarily need to be cured at high temperatures. However, these adhesives can also be harmful to handle and do not have natural ingredients as a base.

Other adhesives are based on PVA, bitumen, inorganic polyurethane binders and/or polyacrylates.

Statement of the Invention

Accordingly, it has been an object of the present invention to provide a method for bonding the surfaces of two or more elements to each other, wherein at least one of the two or more elements is a mineral wool element, the method using an adhesive that does not require high temperatures to cure and In this way, during the handling, application and curing of the adhesive, exposure to hazardous substances is minimized, and protective measures are not mandatory.

According to a first aspect of the present invention, there is provided a method for bonding the surfaces of two or more elements to each other, wherein at least one of the two or more elements is a mineral wool element, said elements being held together with a mineral wool binder, the method comprising the following steps:

- provision of two or more elements,

- applying an adhesive to one or more surfaces to be joined before, during or after bringing the surfaces to be joined into contact with each other,

curing the adhesive, wherein the adhesive contains

- at least one protein,

- at least one phenol- and/or quinone-containing compound and/or at least one enzyme.

In accordance with the second aspect of the present invention provides a product obtained by the described method.

It has been found that the use of this particular type of adhesive, especially if it has the advantageous features set forth, provides particularly durable joints of mineral wool elements.

The inventors of the present invention have surprisingly found that using the method described, it is possible to bond the surfaces of mineral wool elements to each other, or to bond one or more mineral wool elements to another element. Since the adhesive used in the method, in some embodiments, usually does not contain any harmful substances and usually does not emit any harmful substances when cured, the method can be performed by anyone on site without any protective equipment and without the need for special training in the implementation of the method.

Description of Preferred Embodiments

A method of bonding the surfaces of two or more elements to each other, wherein at least one of the two or more elements is a mineral wool element, said elements being held together with a mineral wool binder, the method comprising the following steps:

- provision of two or more elements,

- applying an adhesive to one or more surfaces to be joined before, during or after bringing the surfaces to be joined into contact with each other,

curing the adhesive, wherein the adhesive contains

- at least one protein,

- at least one phenol- and/or quinone-containing compound and/or at least one enzyme.

In a preferred embodiment, the adhesive is applied to one or more surfaces to be bonded prior to bringing the surfaces to be bonded into contact with each other,

The method according to the invention can be used both for connecting two or more mineral wool elements to each other, such as insulating panels, and for connecting one or more mineral wool elements to one or more non-rock wool elements. .

In one embodiment, the two or more elements connected to each other are two or more mineral wool elements.

In another embodiment, the two or more elements to be connected to each other include at least one element that is not a mineral wool element.

Surprisingly, it has been found that the adhesive used in the method according to the present invention can be used not only to bond rock wool elements to each other, but also to bond one or more rock wool elements to a non-rock wool element. .

In one preferred embodiment, at least one non-rock wool element is selected from the group consisting of fleece, wall, drywall, metal, plastic, wood, metal, plastic pipes and/or conduits.

mineral wool element

Rock wool elements generally contain man-made vitreous fibers (MMVF) such as, for example, glass fibers, ceramic fibers, basalt fibers, slag wool, rock wool and stone wool, which are bonded with a hardened mineral wool binder such as thermosetting polymeric 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.

If necessary, the web can be molded before curing. The bonded mineral fiber element can be cut into a desired format, such as a web. Thus, mineral wool elements are, for example, in the form of woven or non-woven material, mats, webs, plates, sheets, plates, strips, rolls, granules and other molded products, which can be used, for example, as thermal or sound insulation materials, vibration absorbers, building materials, façade insulation, roof and floor reinforcing materials, as a filter material, as a growing medium for crops and other applications.

Binder for mineral wool

The mineral wool binder has traditionally 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 regulations to reduce or eliminate formaldehyde emissions have led to the development of formaldehyde-free binders.

One group of non-phenol-formaldehyde binders are 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.

Another group of phenol-formaldehyde-free binders are sugar-based binders, such as those described in EP2990494A1, PCT/EP2015/080758, WO2007/014236, WO2011/138458 and WO2009/080938.

Another group of binders are binders containing at least one protein and at least one enzyme.

Another group of binders are binders containing at least one phenol and/or quinone-containing compound and at least one protein.

Adhesive for use in the method of the present invention

In one preferred embodiment, the adhesive contains at least 70 wt.% protein based on the total solids content of the adhesive.

In a further preferred embodiment, the adhesive further comprises at least one additive.

Preferably, the adhesive is cured at temperatures of 5-95°C, eg 5-80°C, eg 10-60°C, eg 20-40°C.

In one preferred embodiment, the process of curing the adhesive includes a drying process, in particular by blowing air or gas over one or more elements or by increasing the temperature.

The adhesive used in the method of the present invention contains protein as one essential constituent.

Preferably the protein component of the adhesive is in the form of one or more proteins selected from the group consisting of proteins of animal origin, including collagen, gelatin, hydrolyzed gelatin, and proteins from milk (casein, whey), eggs; plant-derived 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; protein-polyphenolic complexes, such as bivalve smooth muscle 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.

Adhesive based on a protein component and a phenol- and/or quinone-containing component

In one embodiment, the present invention relates to a method of bonding the surfaces of two or more elements to each other, wherein at least one of the two or more elements is a mineral wool element, said mineral wool elements being bonded with a mineral wool binder, wherein This method includes the following steps:

- provision of two or more elements,

- applying an adhesive to one or more surfaces to be joined before, during or after bringing the surfaces to be joined into contact with each other,

curing the adhesive, wherein the adhesive contains

- at least one protein,

- at least one phenol and/or quinone-containing compound.

The adhesive according to this embodiment of the present invention contains a phenol- and/or quinone-containing component compound, in particular one or more phenol-containing compounds and/or one or more quinones.

Phenol-containing compounds or phenolic compounds are compounds having one or more hydroxyl groups connected directly to the aromatic ring. Polyphenols (or polyhydroxyphenols) are compounds having more than one phenolic hydroxyl group attached to one or more aromatic rings. Phenolic compounds are characteristic of plants and usually occur in esters or glycosides as a group rather than as free compounds.

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

Preferably, the phenol-containing compound is in the form of one or more components selected from the group consisting of compounds with a C ₆ structure, such as simple phenolic compounds such as resorcinol, phloroglucinol; compounds with a C ₆ -C ₁ structure such as hydroxybenzoic acids such as p-hydroxybenzoic acid, gallic acid, protocatechuic acid, salicylic acid, vanillic acid such as hydroxybenzoic aldehydes such as vanillin; C ₆ -C ₂ compounds such as hydroxyacetophenones such as 2-hydroxyacetophenone such as hydroxyphenylacetic acids such as 2-hydroxyphenylacetic acid C ₆ -C ₃ compounds such as cinnamic acids such as p-coumaric acid, caffeic acid, ferulic acid, 5-hydroxyferulic acid, sinapoic acid, such as esters of cinnamic acid, such as chlorogenic acid, sinapoyl malate, sinapoyl choline, such as cinnamic aldehydes, such as cinnamyl alcohols, such as coumarins, for example, umbelliferone, 4-methylumbelliferone such as isocoumarins such as berginine such as chromones; compounds with a C ₁₅ structure, such as flavonoids, such as flavanone, isoflavones, isoflavanones, neoflavanoids, such as chalcones, such as butein, such as dihydrochalcones, such as phloridzin, such as aurones, such as flavanones, such as naringenin, such as flavanonols such as taxifolin such as flavans such as leucoanthocyanidins such as leukocyanidin, leucodelphinidin such as flavan-3-ols such as catechin, gallocatechin such as flavones such as kaemferol, quercetin, myricetin such as anthocyanidins, such as pelargonidin, cyanidin, peonidin, delphinidin, petunidin, malvidin, such as deoxyanthocyanidins, such as apigeninidin, luteolinidine, 7-methoxyapigeninidin, 5-methoxyluteolinidine, such as anthocyanins, such as petanin, such as a compound with a C ₃₀ structure, such as biflavonyls, such as ginkgetin, such as a compound with a C ₆ -C ₁ -C ₆ structure, such as benzophenones, such as xanthones, such as a compound with a C ₆ -C ₂ -C structure ₆ , such as stilbenes, such as resveratrol, pinosylvin, such as a compound with a C ₆ /C ₁₀ /C ₁₄ structure, such as benzoquinones, such as naphthaquinones, such as juglone, such as anthraquinones, such as emodin, such as a compound with C ₁₈ structure such as betacyanins such as betanidine such as polyphenols and/or polyhydroxyphenols such as lignans, neolignans (dimers or oligomers from the binding of monolignols such as p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol), such as pinoresinol , sesamin, plicic acid, such as lignins (synthesized predominantly from the monolignol precursors of p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol), such as tannins, such as condensed tannins (proanthocyanidins), such as procyanidin B ₂ , such as hydrolysable tannins, such as gallotannins, such as ellagitannins, such as complex tannins, such as acutissimin A, such as tannic acid, such as flobabens.

In a preferred embodiment, the phenol-containing compound is selected from the group consisting of simple phenolic compounds, phenol-containing compounds with a structure more complex than C ₆ such as oligomers of simple phenolic compounds, polyphenols and/or polyhydroxyphenols.

Quinones are oxidized derivatives of aromatic compounds and can often be easily obtained from reactive aromatic compounds with electron-donating substituents, such as phenolic compounds. Quinones that can be used in the present invention include benzoquinones, naphthoquinone, anthraquinone and lawson.

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

Tannins are a group of compounds, very diverse in structure, which have in common the ability to bind and precipitate proteins. Tannins are found in abundance in various types of plants, in particular in oak, chestnut, staghorn sumac and tellima grandiflora. Tannins can be present in leaves, bark and fruits. Tannins can be divided into three groups: condensed tannins, hydrolysable tannins and complex tannins. Condensed tannins or proanthocyanidins are oligomeric or polymeric flavonoids composed of flavan-3-ol (catechin) units. Gallotannins are hydrolysable tannins in which the polyol core contains 10–12 gallic acid residues as substituents. The most common polyol in gallotannins is D-glucose, although some gallotannins contain catechin and triterpenoid units as nuclear polyols. Ellagitanins are hydrolysable tannins that differ from gallotannins in that they contain additional C–C bonds between adjacent haloyl residues. Complex tannins are defined as tannins in which a catechin unit has a glycosidic bond to a gallotannin or ellagitanine unit.

The inventors have surprisingly found that a wide variety of such phenol and/or quinone containing compounds can be used to crosslink proteins to form a binder composition. Often such phenol and/or quinone containing compounds are obtained from plant tissues and are therefore a renewable material. In some embodiments, the compounds are also non-toxic and non-corrosive. As a further advantage, these compounds are antimicrobial and therefore impart their antimicrobial properties to the mineral wool product bonded with such a binder.

In a preferred embodiment, the phenol and/or quinone containing compound is selected from one or more of the group consisting of tannic acid, ellagitannins and gallotannins, tannin derived from one or more of oak, chestnut, staghorn sumac and tellima grandiflora.

In a particularly preferred embodiment, the phenol and/or quinone compound component is tannin and/or tannic acid and the protein component is gelatin, in particular pigskin gelatin, in particular medium or low gel strength.

Without being limited by any particular theory, the inventors believe that the reaction between a phenol and/or quinone containing compound and a protein is based at least in part on the oxidation of phenols to quinones followed by nucleophilic attack on the amine and/or thiol groups of the protein, which leads to cross-linking of proteins with phenol- and/or quinone-containing compounds.

In a preferred embodiment, the content of the phenol and/or quinone-containing compound in the adhesive according to the present invention is from 1 to 70 wt.%, for example from 2 to 60 wt.%, for example from 3 to 50 wt.%, for example from 4 to 40% by weight, for example 5 to 35% by weight, based on the dry weight of the protein.

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

The present inventors have found that adhesive curing is accelerated under alkaline conditions. Therefore, in one embodiment, the mineral fiber adhesive comprises a pH adjuster, preferably in the form of a base, eg an organic base, eg an amine or a salt thereof, inorganic bases, eg a metal hydroxide, eg KOH or NaOH, ammonia or a salt thereof.

In a particularly preferred embodiment, the pH adjuster is an alkali metal hydroxide, in particular NaOH.

In a preferred embodiment, the adhesive according to the present invention has a pH value of 7-10, eg 7.5-9.5, eg 8-9.

In one embodiment, the protein contains protein-polyphenol complexes.

Such 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.

In a preferred embodiment, the adhesives in accordance with the present invention contain additives.

Additives can be other additives, such as one or more reactive or non-reactive silicones, which can be added to the adhesive. 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, amine, epoxy or vinyl functional group capable of reacting with at least one of the components of the adhesive, preferably present in an amount of 0.1-15 wt.%, preferably 0.1-10 wt.%, more preferably 0.3- 8 wt.%, based on the total weight of the adhesive.

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

As already described above, many polyphenols have antimicrobial properties and therefore confer antimicrobial characteristics to the adhesive. However, in one embodiment, an anti-fouling agent may be added to the adhesives.

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

In one embodiment, the adhesive of the present invention contains additives in the form of amine crosslinkers and/or thiol/thiolate crosslinkers. Such additives in the form of amine crosslinkers and/or thiol/thiolate crosslinkers are particularly useful when the crosslinking reaction of the adhesive proceeds along the quinone-amine and/or quinone-thiol pathway.

In one embodiment, the adhesives in accordance with the present invention contain an additive containing metal ions, such as iron ions.

In protein-polyphenol complexes, such as the bivalve adhesive protein described above, 3,4-dihydroxyphenyl residues are used to improve surface adhesion. This is achieved in combination with the secretion of certain types of cations, such as iron ions. In one embodiment, the adhesive can be said to mimic a protein-polyphenol complex, and therefore different cations can improve adhesive properties. Such beneficial ions can also be released from the surface of the mineral fibers upon contact with the water-based adhesive.

In one embodiment, the mineral wool elements bonded by the method of the present invention include stone wool. Without being limited by theory, it is believed that the leaching of certain ions from the vitreous fibers may contribute to the strength of the adhesive. The mechanism may be similar to that by which the bivalve protein provides adhesion to the surface. This is achieved in combination with the secretion of certain types of cations, such as iron ions.

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

Oxidizing agents as additives may be intended to increase the rate of oxidation of polyphenols. An example is the enzyme tyrosinase, which oxidizes phenols to hydroxyphenols/quinones and hence speeds up the adhesive formation reaction. In another embodiment, the oxidizing agent supplied to the adhesive is oxygen.

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

Adhesive based on a protein component and an enzymatic component

In an alternative embodiment, the adhesive used in the method of the present invention is based on a protein component and an enzymatic component.

According to the present embodiment, the invention relates to a method for bonding the surfaces of two or more elements to each other, wherein at least one of the two or more elements is a mineral wool element, said mineral wool elements being bonded with a mineral wool binder, wherein the method includes the following steps:

- provision of two or more elements,

- applying an adhesive to one or more surfaces to be joined before, during or after bringing the surfaces to be joined into contact with each other,

curing the adhesive, wherein the adhesive contains

- at least one protein,

- and/or at least one enzyme.

In a preferred embodiment, the enzymatic adhesive 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 having a medium gel strength, and the enzyme component is transglutaminase (EC 2.3.2.13).

The present inventors have found that, in some embodiments, the method of the present invention is best performed if the adhesive based on the protein component and the enzymatic component is applied under acidic conditions.

Thus, in a preferred embodiment, the adhesive contains a pH adjuster, in particular in the form of a pH buffer.

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

The other 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, amine, epoxy or vinyl functional group capable of reacting with at least one of the components of the adhesive, preferably present in an amount of 0.1-15 wt.%, preferably 0.1-10 wt.%, more preferably 0.3- 8 wt.%, based on the total weight of the adhesive.

In one embodiment, a silane can be added to the adhesive.

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

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

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

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

In one embodiment, the adhesive in accordance with the present invention contains additives in the form of cross-linking agents containing acyl groups and/or amino groups and/or thiol groups. These crosslinkers can reinforce and/or modify the polymer network of the cured adhesive.

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

Adhesive bonding process

In one embodiment, after the adhesive has been applied, the elements are pressurized during bonding, and preferably the total time for applying the adhesive and applying pressure does not exceed 120 seconds, such as 60 seconds, such as 30 seconds, such as 20 seconds.

In one embodiment, the panels can be moved along the fixed nozzles, or the fixed panels can be sprayed or rolled. The time for spraying and bonding with the adhesive is a maximum of 120 seconds. The panels are pressed together after spraying an adhesive onto them.

In one embodiment, the adhesive may be applied to only one of the surfaces to be bonded, but it may be applied to both surfaces.

In one embodiment, the protein component of the adhesive can be applied to the first surface to be bonded, and the compound containing the phenol and/or quinone and/or at least one enzyme can be applied to the second surface to be bonded, then the first and second surfaces are brought into contact with each other. with a friend.

The advantage would be to achieve a balanced penetration of the adhesive into the deeper layers of the element; such a connection will be more durable than a connection made by a different method. Typically, the adhesive does not penetrate the element deeper than 2 mm.

In one embodiment, the consumption of the cured adhesive by surface area is 10-1000 g/m ² , eg 50-500 g/m ² , eg 100-400 g/m ² .

In one embodiment, the adhesive is applied with a spray gun, roller, brush, flow coat, sponge, or soft sponge roller.

Product

The present invention also relates to a product made as described above, for example, a product in which at least one of the elements is a mineral wool element.

In a preferred embodiment, the product contains at least one element which is a mineral wool product, wherein the density of the mineral wool product is in the range of 10-1200 kg/m ³ , for example 30-800 kg/m ³ , for example 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 one embodiment, the product obtained as described above is a product in which the mineral wool product comprises a fleece bonded to a mineral wool element in the manner described above.

mineral wool product

In one embodiment, two or three (and in some cases more) elements can be fastened together to form an insulating panel. The elements are connected together by the largest surfaces. For example, the bottom surface of the first element is connected to the top surface of the second element, and the bottom surface of the second element is connected to the top surface of the third element. Alternatively, in another embodiment, the base surfaces can be bonded whether they are top or bottom.

The proposed insulating panels can be used to insulate various surfaces, including roofs, exterior walls of buildings and ceilings. They can be used as acoustic, thermal or fire insulation.

In one embodiment, the flat roof structure is insulated with mineral wool insulating elements, the elements being laid on the flat surface in two layers, with a top and bottom layer, and the elements of the top layer being bonded to the elements of the bottom layer with an adhesive.

In one embodiment, the outer or inner wall is insulated with mineral wool insulating elements, the elements being placed on the outer or inner wall in two layers, a wall-facing layer and an outward-facing layer, and the elements of the wall-facing layer being attached to the layers. facing outward with an adhesive. An exterior wall insulated in this manner may form part of an exterior thermal insulation composite system (ETICS).

Granular product

In one embodiment, the mineral wool product is a granular product. The granular product is typically made by providing a cured rock wool web and then subjecting the web to a granulation process that forms granules. The granules are typically 1-5 cm in size and the binder content is the LOI value, which is typically around 1%. The granules are packaged in a compressed state, then the package is opened at the construction site to apply the granular product using blow molding equipment, such as a horizontal loft, between walls or another structure.

The adhesive is applied before or during the application of the granular product, whereby the granules, which are mineral wool elements, are bonded to each other. The granules and adhesive form a granular mineral wool product having improved properties such as being less prone to dusting and forming a stiffer structure that is less likely to compress under its own weight.

In an alternative embodiment, the granules and adhesive form a granular mineral wool product that is attached to a building structure, such as a wall or ceiling, such that the mineral wool product completely or partially covers the building structure.

Sandwich panel product

In one embodiment, the mineral wool product is the core of a so-called sandwich panel. The core of the sandwich panel can be produced in a general way, in which the cured rock wool web is cut longitudinally into elements that are lamellae, and the lamellae thus formed are rotated 90° about their longitudinal axis, after which the thus oriented panels are bonded to each other with an adhesive to forming a web-like product, which is then cut to the required length to form plate elements. Due to the rotation of the lamellae, the fibers of the finished boards will generally be oriented in a plane perpendicular to the board surfaces, resulting in boards having significant stiffness and strength perpendicular to the board surfaces.

To provide a sandwich panel product, the core is provided with, for example, metal sheets on the main surfaces of the panel by gluing them with an adhesive.

Mineral wool product with fleece content

One or both surfaces, for example the main surface of a mineral wool product or element, can be applied with an adhesive, then the fleece is brought into contact with said surface and the adhesive is allowed to cure. Alternatively or in addition, the adhesive may be applied to the fleece prior to contact.

Elements other than fleece can be attached to mineral wool products or elements using the process steps of the present invention.

These other elements can be a wall, drywall, metal, plastic.

Examples

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

Products made using prior art binders

Two stone wool roof slabs with densities of approximately 150 kg/m ³ were made using two different binders (Binder A and Binder B, see mixing examples below) according to the prior art.

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. 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.

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).

Binder Example, Binder A (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 is prepared by adding 25% aq. ammonia solution (90 ml) and ammonium sulfate (13.2 g) and then water (1.30 kg). The binder solids were then measured as described above and the mixture was diluted with the required amount of water and silane (0.5% silane based on binder solids, Momentive VS-142).

Example of binder, binder B

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). The binder solids were then measured as described above (21.5%) and the mixture was diluted with the required amount of water and silane (0.5% silane based on binder solids, Momentive VS-142). The finished binder mixture had a pH of 7.0.

Adhesives in accordance with the present invention

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

Reagents

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

Solids content of adhesive components, determination

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

Adhesive Example, Binder 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. 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. This adhesive mixture had an adhesive solids content of 14.5%.

Adhesive Example, Adhesive 2

To a solution of 1 M NaOH (12.0 g) was added tannic acid (2.0 g) at room temperature. The resulting mixture was stirred for 15 minutes, after which a brown-greenish solution was obtained.

Medium strength pigskin gelatin (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 4.9) was obtained. Next, 1 M NaOH (3.00 g) (pH 8.9) was added, followed by tannic acid in aq. NaOH solution (7.0 g, prepared as described above). The mixture was vigorously stirred for 30 minutes at 50° C. and the resulting brown mixture (pH 8.7) was then used in further experiments. This adhesive mixture had an adhesive solids content of 14.8%.

Examples according to the present invention

Samples of 8 cm × 5 cm × 3 cm (length, width, height) or 8 cm × 5 cm × 5 cm (length, width, height) were cut from stone wool roof panels obtained using binder A and B.

Connecting and testing specimens

In each joint test, one sample of the roof slab made using binder A and one sample of the roof slab made using binder B were placed on a flat surface with one of the 8 cm × 5 cm sides facing up. A sample of Adhesive 1 or 2 (2.5 g, as described above) was then placed on the top surface of each of the two roof panel samples. The adhesive mixture was spread evenly over the surfaces using a plastic spatula. The adhesive mixture could penetrate the surfaces by 1-2 mm. One of the two board samples was then placed on top of the other so that the two surfaces coated with adhesive 1 or 2 came into contact with each other. A weight of about 200 g was placed on top of the connected roof slab samples and the assembly was left for 2-3 days at room temperature. The glued samples were further cut into two halves so that one half of the glued sample could be subjected to aging tests.

Two such joint tests were performed using Adhesive 1 and two joint tests were performed using Adhesive 2.

The samples selected for aging were immersed in a water bath at 80°C for 3 h.

After drying for about a week at room temperature, the selected samples were separated in a direction perpendicular to the newly bonded surfaces.

Samples made with Adhesive 1 subjected to the aged treatment ruptured at the joint where Adhesive 1 was applied after the adhesive dissolved during the aged treatment (see FIG. 1, left). Samples made with Adhesive 2, subjected to aging treatment, instead ruptured in rock wool layers that were not in contact with Adhesive 2 (see Fig. 1, right).

On FIG. 1 shows bonded roof slab samples made with bonding agent A (upper portions) and bonding agent B (lower portions), (a) and (b): bonded using adhesive 1; (b) aged and then stretched in a direction perpendicular to the bonded surfaces, (c) and (d): bonded using adhesive 2; (d) subjected to an aging effect followed by stretching in a direction perpendicular to the joined surfaces.

Claims (27)

1. A method of bonding the surfaces of two or more elements to each other, wherein at least one of the two or more elements is a mineral wool element, said mineral wool elements being bonded with a mineral wool binder, the method comprising the following steps: - providing two or more elements, - applying an adhesive to one or more surfaces to be joined before, during or after bringing the surfaces to be joined into contact with each other, curing the adhesive, the adhesive comprising: - at least one protein, - at least one phenol- and/or quinone-containing compound and/or at least one enzyme, and the content of phenol - and/or quinone-containing compounds in the adhesive is from 1 to 70 wt. %, for example from 2 to 60 wt. %, for example from 3 to 50 wt. %, for example from 4 to 40 wt. %, for example from 5 to 35 wt. %, based on dry weight of protein, and 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). 2. Method according to claim 1, characterized in that the two or more elements are two or more mineral wool elements. 3. Method according to claim 1, characterized in that the two or more elements include at least one element which is not a mineral wool element. 4. The method according to claim 3, characterized in that at least one element, which is not a mineral wool element, is selected from the group consisting of a fleece, such as a fiberglass fleece, a building structure, such as a wall, ceiling, roof. 5. The method according to any one of the preceding claims, characterized in that the adhesive further comprises at least one additive. 6. Method according to any one of the preceding claims, characterized in that curing is carried out at temperatures from 5 to 95°C, for example from 5 to 80°C, for example from 10 to 60°C, for example from 20 to 40°C. 7. Method according to any one of the preceding claims, characterized in that the curing comprises a drying process, in particular by blowing air or gas over the mineral wool product or by raising the temperature. 8. The method according to any of the preceding paragraphs, characterized in that 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. 9. The method according to claim 8, characterized in that the collagen or gelatin preferably comes from one or more sources from the group consisting of mammalian and avian species such as cow, pig, horse, poultry, and / or from scales, skin fish. 10. The method according to any one of the preceding claims, characterized in that at least one phenol and/or quinone containing compound contains a phenol containing compound such as simple phenolic compounds such as hydroxybenzoic acids such as hydroxybenzoic aldehydes such as hydroxyacetophenones such as hydroxyphenylacetic acids such as cinnamic acids such as cinnamic acid esters such as cinnamic aldehydes such as cinnamyl alcohols such as coumarins such as isocoumarins such as chromones such as flavonoids such as chalcones such as dihydrochalcones such as aurones such as flavanones such as flavanonols such as flavans such as leucoanthocyanidins such as flavan-3-ols such as flavones such as anthocyanidins such as deoxyanthocyanidins such as anthocyanins such as biflavonyls such as benzophenones such as xanthones such as stilbenes such as benzoquinones such as naphtaquinones such as anthrachs nones such as betacyanins such as polyphenols and/or polyhydroxyphenols such as lignans, neolignans - dimers or oligomers from the binding of monolignols such as p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol such as lignins - synthesized predominantly from monolignolic precursors p -coumaryl alcohol, coniferyl alcohol and sinapyl alcohol, such as tannins, such as condensed tannins, proanthocyanidins, such as hydrolysable tannins, such as gallotannins, such as ellagitannins, such as complex tannins, such as tannic acid, such as flobabens, and/or a quinone-containing compound such as benzoquinones such as naphthaquinones such as anthraquinones such as lawson. 11. The method according to claim 10, in which the tannin is 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 large-flowered tellima. 12. The method according to any of the above paragraphs, characterized in that the phenol and/or quinone-containing compound contains one or more synthetic or semi-synthetic molecules, including phenols, polyphenols, quinones, such as proteins, peptides, peptoids or arylopeptoids, modified with phenol and/or quinone containing side chains, such as dendrimers with phenol and/or quinone containing side chains. 13. The method according to any of the above paragraphs, characterized in that the tannin content is from 1 to 70 wt. %, for example from 2 to 60 wt. %, for example from 3 to 50 wt. %, for example from 4 to 40 wt. %, for example from 5 to 35 wt. %, based on the dry weight of the protein. 14. The method according to any of the above paragraphs, in which the mass ratio of (lysine + cysteine) in protein to (phenol + quinone) in a phenol- and / or quinone-containing compound is 1:5.78-1:0.08, for example 1:2.89-1:0.09 e.g. 1:1.93-1:0.12 e.g. 1:1.45-1:0.15 e.g. 1:1.16-1:0.17 . 15. The method according to any of the above, characterized in that the adhesive further comprises an additive selected from the group consisting of an oxidizing agent such as tyrosinase, a metal ion such as an iron ion, a pH adjuster, preferably in the form of a base, such as an organic base, for example an amine or a salt thereof, inorganic bases such as a metal hydroxide such as KOH or NaOH, ammonia or a salt thereof. 16. The method according to any of the above, characterized in that the adhesive has a pH value of from 7 to 10, for example from 7.5 to 9.5, for example from 8 to 9. 17. The method according to any of the above paragraphs, characterized in that the adhesive contains at least one additive selected from the group consisting of cross-linking agents containing acyl groups and/or amine groups and/or thiol groups. 18. The product obtained by the method according to any one of paragraphs. 1-17. 19. The product according to claim 18, which is a mineral wool product, characterized in that the density of the mineral wool product is in the range of 10-1200 kg/m ³ , for example 30-800 kg/m ³ , for example 40-600 kg/ m ³ eg 50-250 kg/m ³ eg 60-200 kg/m ³ . 20. The product according to claim 18 or 19, characterized in that the mineral wool product contains a fleece attached to the mineral wool element by the method according to any one of paragraphs. 1-17.

Images