WO2014170481A1

WO2014170481A1 - Binders

Info

Publication number: WO2014170481A1
Application number: PCT/EP2014/058005
Authority: WO
Inventors: Lidija MIRNIK; Jovica MISIC; Gavro MILINKOVIC; Markus Mente
Original assignee: Knauf Insulation
Priority date: 2013-04-19
Filing date: 2014-04-18
Publication date: 2014-10-23
Also published as: GB201307095D0; GB2515619B; GB2515619A; GB201407008D0

Abstract

The present invention relates to a nanoparticle-containing binder composition, a method of producing a mineral fibre product employing said binder composition, a method of producing a mineral product, a mineral fibre product comprising nanoparticles, and the use of nanoparticles in the manufacture of a mineral fibre product.

Description

BINDERS

The present invention relates to a nanoparticle-containing binder composition, a method of producing a product, notably a mineral fibre product, employing said binder composition, a method of producing a mineral product, a product, notably a miner- al fibre product comprising nanoparticles, and the use of nanoparticles in the manufacture of a mineral fibre product.

Mineral fibre products find significant use e.g. as acoustic or thermal insulation material in a wide variety of commercial applications. Generally, mineral fibre products are manufactured by applying a binder composition, such as a phenol-formaldehyde based binder composition or a substantially formaldehyde free binder composition, to mineral fibres and curing the binder-coated mineral fibres. During the curing step, the binder composition dispersed on the mineral fibres polymerizes to form a cured resin that binds the mineral fibres together to impart strength and resiliency to the mineral fibre product. The resulting mineral fibre products thus retain their shape due to resin crosslinking of the mineral fibres.

On-going research and development is directed to improve the binder compositions useful in the manufacturing of mineral fibre products, particularly in view of improved chemical, mechanical and thermal properties, such as improved stability against moisture and higher tensile resistance, compressive and sheer strengths, lower thermal conductivity, improved point load, etc. For environmental and economic reasons, there is a high demand for novel binder compositions which can provide the above-mentioned chemical and mechanical properties when using less binder in the final product.

Accordingly, the technical problem underlying the present invention is to provide binder compositions, particularly usable in the manufacture of mineral fibre products, which can increase the afore-mentioned chemical, mechanical and/or thermal prop- erties of said mineral fibre products, and/or which allow a reduction in the amount of binder used while maintaining the above-mentioned desirable properties of the min- eral fibre products.

In order to solve the above technical problem, as a first aspect, the present invention provides a method of manufacturing a mineral wool product as defined in claim 1 . Further aspects of the invention relates to a binder composition comprising

(a) one or more curable binder component(s), and

(b) nanoparticles

and to use of such a binder composition. As used herein the term "mineral fibre" refers to any fibres made from natural or synthetic minerals. Such mineral fibres include glass fibres, stone wool fibres, slag fibres and ceramic fibres. The compositions of such mineral wool fibres may comprise (by % weight):

In the case of stone wool mineral fibres, the ratio of alkali/alkali earth expressed in the form of oxides is preferably <1 and/or the proportion of R2O (Na2O + K2O) may be 9-15 %, preferably 10-14%. The mineral wool insulation products may have a density which is:

• at least 25 kg/m³, at least 50 kg/m³, at least 80 kg/m³, at least 90 kg/m³, at least

100 kg/m³, at least 1 10 kg/m³ or at least 120 kg/m³ and/or

• no more than 280 kg/m³, no more than 250 kg/m³, no more than 230 kg/m³, no more than 200 kg/m³,no more than 180 kg/m³ or no more than 160 kg/m³.

Such density provides desirable mechanical characteristics notable compression strength and/or tensile strength and/or point load and/or sheer strength and/or water repellency. As used herein, the term "binder composition" generally includes one or more curable binder components and nanoparticles, which may be used as a binder for binding mineral fibres.

As used herein, the expression "one or more curable binder component(s)" refers to any component, or mixture of components, which may be cured, e.g. by thermal and/or catalytic or/and pressure treatment, to form a resin that is suited to bind e.g. mineral fibres via crosslinking. Such binder components include organic and inorganic binder systems. Such components, or mixture of components, include any organic or inorganic binder component, as well as mixtures thereof, which can be cured to form a resin, either individually or together. Examples of such binder components, or mixtures thereof, include (i) phenol-formaldehyde, (ii) phenol-melamine, (iii) urea-formaldehyde, (iv) polyvinyl acetate (PVA), and (v) at least one carbohydrate component with at least one amine component, which can polymerize in a Mail lard-type reaction, such as known from e.g. WO 201 1/138458 A1 and WO 201 1/138459 A1 . According to one embodiment of the present invention, the binder composition comprises phenol and formaldehyde as binder components. In addition, the binder composition may comprise a silane and/or a dedusting agent (for example a mineral oil and/or vegetable oil and/or silicone oil) and/or a wetting agent (for example polyethylene glycol and/or other surfactant and/or ammonia sulfate) and/or a melamine and/or a carbohydrate component. According to another embodiment of the present invention, the binder composition comprises at least one carbohydrate component and at least one amine component which can polymerize in a Mail lard-type reaction.

The binder components may comprise reducing sugar(s) and/or reaction products of at least one carbohydrate component and at least one amine component. The carbohydrate component may comprise a monosaccharide in its aldose or ketose form or one or more reducing sugars; it may have a dextrose equivalent of at least about 50, at least about 60, at least about 70, at least about 80 or at least about 90. The amine component may comprise NH3, inorganic amine(s), organic amine(s) compris- ing at least one primary amine group, salts thereof and combinations thereof; it may comprise a polyamine, notably having two or more primary amine groups (-NH2). The reducing sugar or carbohydrate component may make up: at least 30%, preferably at least 40%, preferably at least 50%, more preferably at least 60%, more preferably at least 70%, even more preferably at least 80% by dry weight of the uncured binder composition; and/or less than 99%, preferably less than 97%, more preferably less than 95 % by dry weight of the uncured binder composition. The amine component, when present, may make up less than 70%, preferably less than 50%, more preferably less than 30%, even more preferably less than 20% by dry weight of the uncured binder composition; and/or at least 2.5%, preferably at least 5%, more pref- erably at least 10% by dry weight of the uncured binder composition.

The amount of the one or more curable binder component(s), based on the total weight of the binder composition (which is expressed herein notably as dry weight of the one or more curable binder component(s) with respect to total dry weight of the binder composition) includes ranges from 50 to 99.99 wt.-%, from 50 to 95 wt.-%, from 50 to 90 wt.-%, from 50 to 85 wt.-%, from 50 to 80 wt.-%, from 50 to 75 wt.-%, from 50 to 70 wt.-%, from 50 to 65 wt.-%, from 50 to 60 wt.-%, and from 50 to 55 wt.- %. Other examples include ranges of from 55 to 99.99 wt.-%, from 60 to 99.99 wt.-%, from 65 to 99.99 wt.-%, from 70 to 99.99 wt.-%, from 75 to 99.99 wt.-%, from 80 to 99.99 wt.-%, from 85 to 99.99 wt.-%, from 90 to 99.99 wt.-%, and from 95 to 99.99 wt.-%. According to a specific embodiment, the amount of the one or more curable binder component(s), based on the total weight of the binder composition, includes ranges from 96 to 99.99 wt.-%, from 97 to 99.99 wt.-%, from 98 to 99.99 wt.-%, from 98.5 to 99.99 wt.-%, from 99 to 99.99 wt.-%, from 99.25 to 99.99 wt.-%, from 99.5 to 99.99 wt.-%, from 99.75 to 99.99 wt.-%, and from 99.90 to 99.99 wt.-%. According to another specific embodiment, the amount of the one or more curable binder compo- nent(s), based on the total weight of the binder composition, includes ranges from 95 to 99.95 wt.-%, from 95 to 99.90 wt.-%, from 95 to 99.85 wt.-%, from 95 to 99.75 wt.- %, from 95 to 99.5 wt.-%, from 95 to 99 wt.-%, from 95 to 98.5 wt.-%, and from 95 to 98 wt.-%. According to the present invention, the upper and lower borders of the above-mentioned amount ranges may be freely combined.

According to a particularly preferred embodiment of the present invention, the amount of the one or more curable binder component(s) is from 95 wt.-% to 99.99 wt.-%, based on the total weight of the binder composition. As used herein, the term "nanopartides" includes any inorganic particles having a size from 5 nm to 10.000 nm, for example a size in the range of 8 nm to 3000 nm, in the range of 10 nm to 2000 nm or in the range of 12 nm to 500 nm. According to a preferred embodiment, the size of the nanopartides is in the range of 50 to 500 nm. When the binder composition comprising nanopartides is used to bind a collection of mineral fibres in order to form a mineral fibre product, the nanopartides are considered to act as reinforcement in the binder structure, e.g. by assisting in the formation of a desirable resin structure. Moreover, the nanopartides improve the particle distribution into a much more organized and homogeneous structure of particles in a dry resin, or improve the drop formation of resin droplets in the fibre network in solution/dispersion, particularly at intercrossing fibre locations, so that a particularly strongly bound mineral fibre product can be obtained. Without wishing to be bound by theory it is currently thought that the presence of the nanopartides provokes a reduced or better optimized size of resin droplet; this is thought to lead to an in- creased number of intersection between individual fibres being connected with resin droplets so that a particularly strongly bound mineral fibre product can be obtained. Therefore, by addition of nanoparticles to the binder composition it is possible to increase the mechanical properties of the final mineral fibre product by using the same binder amount as in known processes. As an alternative, it is also possible to reduce the amount of binder in the final mineral fibre product to 80% or less, for example to 50% or less, or 30% or less, when compared to the amount of binder used in standard processes, however, without impacting the mechanical and/or thermal properties of the final mineral fibre product.

According to one embodiment of the present invention, the nanoparticles comprise one or more metal oxides. Herein, the term "metal oxide" includes any compound which contains a metal ion and an oxygen ion. However, the expression "metal oxide" used herein further includes any covalently bound compounds of a metal and oxygen.

According to a preferred embodiment, said metal oxides are selected from the group consisting of S1O2, ΤΊΟ2, MgO, AI2O3, MnO, CuO and AgO, as well as mixtures thereof. Alternatively or in addition to the above embodiment, the nanoparticles may be ionic compounds such as salts and/or neutral inorganic or organic materials such as clay or any similar material.

The nanoparticles may be in the form of particles. According to a further embodiment, the nanoparticles of the present invention may be in the form of nanotubes, which will give additional properties (strength) to the binder system and finally to the resulting product. Said nanotubes can be based on e.g. carbon, nitrides (borate), titanium dioxide, sulphides (of molybdenum, tungsten, copper, etc.), halogenides (particularly chlorides and iodides such as N1CI2, CdC and/or Cd ). According to the present invention, the above nanoparticles may be used as single component in the binder composition or as mixtures. The amount of nanoparticles, based on the total weight of the binder composition (which is expressed herein notably as dry weight of nanoparticles with respect to total dry weight of the binder composition) includes ranges from 0.01 wt.-% to 50 wt.-%, from 0.01 to 45 wt.-%, from 0.01 to 40 wt.-%, from 0.01 to 35 wt.-%, from 0.01 to 30 wt.-%, from 0.01 to 25 wt.-%, from 0.01 to 20 wt.-%, from 0.01 to 15 wt.-%, from 0.01 to 10 wt.-%, and from 0.01 to 5 wt.-%. Other examples include ranges of from 5 to 50 wt.-%, from 10 to 50 wt.-%, from 15 to 50 wt.-%, from 20 to 50 wt.-%, from 25 to 50 wt.-%, from 30 to 50 wt.-%, from 35 to 50 wt.-%, from 40 to 50 wt.-%, and from 45 to 50 wt.-%. According to a specific embodiment, the amount of the nanoparticles, based on the total weight of the binder composition, includes ranges from 0.01 to 4 wt.-%, from 0.01 to 3 wt.-%, from 0.01 to 2 wt.-%, from 0.01 to 1 .5 wt.-%, from 0.01 to 1 wt.-%, from 0.01 to 0.75 wt.-%, from 0.01 to 0.5 wt.-%, from 0.01 to 0.25 wt.-%, and from 0.01 to 0.1 wt.-%. According to another specific embodiment, the amount of the nanoparticles, based on the total weight of the binder composition, includes ranges from 0.05 to 5 wt.-%, from 0.1 to 5 wt.-%, from 0.15 to 5 wt.-%, from 0.25 to 5 wt.-%, from 0.5 to 5 wt.-%, from 1 to 5 wt.-%, from 1 .5 to 5 wt.-%, and from 2 to 5 wt.-%. According to the present invention, the upper and lower borders of the above- mentioned amount ranges may be freely combined.

Particularly in embodiments having high amounts of nanoparticles, notably amounts of 20 to 35 wt% of more of nanoparticles, e.g. amounts of 25 wt.-% or more of nanoparticles, based on the total weight of the binder composition, in the binder composi- tion of the present invention, a mineral fibre product obtainable by curing a mixture of mineral fibres and the binder composition exhibits advantageously high thermal insulation properties.

The pH of the nanoparticles, or if applicable, of a solution and/or dispersion contain- ing the nanoparticles of the present invention is not particularly limited and may vary from about 2 to about 14.

The nanoparticles in the binder composition may be applied to the mineral fibres in a solution and/or a dispersion. The dispersion may comprise a suspension of nanopar- tides in a liquid, notably in water; this may be mixed with an emulsion and may comprise an emulsifying agent and/or a dispensing agent and/or a stabiliser. The dispersion may be mixed with the binder composition and/or diluted prior to application to the mineral fibres.

The amount of nanoparticles in the dispersion, based on the total weight of the liquid dispersion, may be:

· Greater than or equal to: 3 wt% or 5 wt% or 10 wt% or 12 wt% or 19 wt%; and or

• Less than or equal to: 60 wt% or 40 wt% or 25 wt% or 20 wt%.

The amount of dispersing agent, based on the total weight of the liquid dispersion may be:

• Greater than or equal to: 0.5 wt% or 1 wt% or 2 wt% or 5 wt%; and or

• Less than or equal to: 18 wt% or 15 wt% or 10 wt%.

The binder composition of the present invention may further comprise ammonia or a salt thereof. Preferably, the ammonia or the salt thereof may be present in an amount of 0.1 to 7 wt.-%, based on the total weight of the binder composition. In case the binder components are phenol-formaldehyde binder components, ammonia or the salt thereof is preferably present in an amount of 0.1 to 0.5 wt.-%, based on the total weight of the binder composition. In case the binder components are at least one carbohydrate component with at least one amine component, which can polymerize in a Mail lard-type reaction, ammonia or the salt thereof is preferably present in an amount of 3 to 5 wt.-%, based on the total weight of the binder composition.

When employing the binder composition of the present invention to produce a miner- al fibre product, the final product may contain fine particulate matter. Therefore, to reduce or avoid release of such fine particulate matter, the binder composition of the present invention further preferably comprises at least one dust oil or dust oil emulsion. For example, the dust oil or dust oil emulsion may be present in the binder composition in an amount of 0 to 2 wt.-%, more preferably of 0.2 to 0.8 wt.-%, based on the total weight of the binder composition. Such dust oils and dust oil emulsions are known to the person skilled in the art and are commercially available, such as Garo 217S, etc. According to a preferred embodiment of the present invention, the binder composition further comprises at least one silane, e.g. an aminosilane. For example, the silane may be present in the binder composition in an amount of 0.001 wt.-% to 0.5 wt.-%, preferably of 0.1 wt.-% to 0.4 wt.-%, based on the total weight of the curable binder components. If the amount of silane in the binder composition is in the above range, the long term strength of the binder, particularly after being weathered, is significantly improved. The binder composition of the present invention may comprise further additives such as water repellent additives, water pickup additives etc.

The binder composition of the present invention preferably has a density of from 0.6 kg/m³ to 2000 kg/m³.

A further aspect of the present invention relates to an aqueous solution and/or dispersion comprising the binder composition as defined above.

Herein, the expression "solution and/or dispersion" includes the case where one or more of the curable binder component(s), as well as the nanoparticles may be completely or partly dissolved in the aqueous solvent, as well as any combination of dissolved and dispersed components.

The amount of the one or more curable binder component(s), based on the total weight of the aqueous solution and/or dispersion of the binder composition (i.e. the total weight of the binder composition and solvent), includes ranges from 5 to 95 wt.- %, from 5 to 90 wt.-%, from 5 to 80 wt.-%, from 5 to 70 wt.-%, from 5 to 60 wt.-%, from 5 to 50 wt.-%, from 5 to 40 wt.-%, from 5 to 30 wt.-%, from 5 to 20 wt.-%, and from 5 to 15 wt.-%. Other examples include ranges of from 10 to 95 wt.-%, from 20 to 95 wt.-%, from 30 to 95 wt.-%, from 40 to 95 wt.-%, from 50 to 95 wt.-%, from 60 to 95 wt.-%, from 70 to 95 wt.-%, from 80 to 95 wt.-%, and from 90 to 95 wt.-%. According to the present invention, the upper and lower borders of the above-mentioned amount ranges may be freely combined.

The amount of the nanoparticles, based on the total weight of the aqueous solution and/or dispersion of the binder composition (i.e. the total weight of the binder compo- sition and solvent), includes ranges from 0.001 to 50 wt.-%, 0.001 to 45 wt.-%, 0.001 to 40 wt.-%, 0.001 to 35 wt.-%, 0.001 to 30 wt.-%, 0.001 to 25 wt.-%, 0.001 to 20 wt.- %, 0.001 to 15 wt.-%, 0.001 to 10 wt.-%, and 0.001 to 5 wt.-%. Other examples include ranges of from 0.01 to 50 wt.-%, from 0.1 to 50 wt.-%, from 0.5 to 50 wt.-%, from 1 to 50 wt.-%, from 3 to 50 wt.-%, from 5 to 50 wt.-%, from 10 to 50 wt.-%, from 15 to 50 wt.-%, from 20 to 50 wt.-%, from 25 to 50 wt.-%, from 30 to 50 wt.-%, from 35 to 50 wt.-%, from 40 to 50 wt.-% and from 45 to 50 wt.-%. According to the present invention, the upper and lower borders of the above-mentioned amount ranges may be freely combined. According to a specific embodiment, the amount of the one or more curable binder component(s), based on the total weight of the aqueous solution and/or dispersion of the binder composition, is from 5 to 40 wt.-%, notably from 5 to 25 wt.-%, preferably from 10 to 20 wt.-%, and the amount of the nanoparticles, based on the total weight of the aqueous solution and/or dispersion of the binder composition, is from 0.01 to 35 wt.-%, notably from 0.01 to 5 wt.-%, preferably from 0.1 to 5 wt.-%.or from 0.1 to 3 wt.-%.

It is currently thought that the nanoparticles act in a binder solution/dispersion as a homogenisation system which can improve the mixing of all ingredients due to at- taching the homogenized mixture of solutions onto their surface and as such form a more spherical particles or drops, and therefore the nanolayer of film is created on the fibre. It is also thought that the nanoparticles in this system provide an improvement by decreasing the size of and increasing the number of droplets of binder solution.

One aspect of the present invention relates to a method of producing a nano-particle- reinforced mineral fibre product, comprising (a) providing mineral fibres formed from a molten mineral;

(b) applying a binder composition or aqueous solution and/or dispersion of binder composition to the mineral fibres;

(c) collecting the mineral fibres to which the binder composition has been applied to form a batt of mineral fibres; and

(d) curing the batt comprising the mineral fibres and the binder composition to obtain a bound mineral fibre product.

Herein, the expression "nanoparticle-reinforced mineral fibre product" includes such mineral fibre products which contain nanoparticles that interact with or promote the binding of the individual mineral fibres by the cured binder composition.

The expression "molten mineral" used herein includes any substances or mixtures of substances in a molten form, which are generally usable in the manufacture of min- eral fibres. These substances include, without being limited thereto, magmatic or/and sedimental stones and/or chemical ingredients, as an example quartz, anorthosid, borax, soda ash, diabase/dolorite, amphiboles, basalts, and dolomites. Other examples include bauxite, alumina oxide, magnesia oxide, alumina compounds and zirco- nia dioxide.

The expression "applying a binder composition" includes any process which is suited to bring the binder in contact with the mineral fibre material. Preferred examples of binder application include spraying the binder composition, e.g. in form of an aqueous solution and/or dispersion or a layer of binder (when there is dry binder applied) onto the mineral fibres or mixing the fibres with such a binder composition.

The binder components and the nanoparticles are preferably applied together to the mineral fibres e.g. by spraying a solution and/or dispersions containing the said binder components and the nanoparticles. This enables a uniform distribution of both the binder components and the nanoparticles throughout the fibre material.

Herein, the step of "curing" includes any means which are suited to polymerize the binder components in the binder composition in order to obtain a cured binder resin. For example, the step of curing may be performed by heat treatment and/or with pressure treatment. According to a further aspect, the present invention relates to a method of producing a nanoparticle-reinforced mineral fibre product, comprising:

(a) providing mineral fibres formed from a molten mineral;

(b) applying a binder composition to the mineral fibres, wherein the binder composition comprises one or more curable binder components, or applying an aqueous so- lution or dispersion of one or more curable binder components;

(c) applying nanopartides to the mineral fibres;

(d) collecting the mineral fibres to which the binder composition and the nanopartides have been applied to form a batt of mineral fibres; and

(e) curing the batt comprising the mineral fibres, the binder composition and the na- noparticles to obtain a bound mineral fibre product.

The application of the nanopartides to the mineral fibres should be performed such that the nanopartides are homogeneously distributed in the mineral fibre product, or are present in form of layers in-between the mineral wool fibres.

The binder composition and the nanopartides may be applied separately to the mineral fibres, for example by simultaneously spraying different solutions and/or dispersions containing the binder components and the nanopartides, respectively, onto the mineral fibres. Alternatively, the nanopartides may be applied to the mineral fibres before or after the binder composition is applied to the mineral fibres. As such, the sequence of steps (b) and (c) in the above-mentioned method is not restricted herein. According to another example, the nanopartides may be applied to the mineral fibres as a powder or a solution and/or dispersion during or after the step of collecting the mineral fibres, e.g. in the collecting chamber.

In a further aspect, the present invention relates to a mineral fibre product, comprising mineral fibres and a cured binder composition as defined above. The amount of nanoparticles in the cured binder composition may be:

• Greater than or equal to: 0.01 wt% or 0.05 wt% or 0.1 wt% or 0.3 wt%; and/or

• Less than or equal to: 6 wt% or 5 wt% or 4 wt% or 2 wt%.

Alternatively, the amount of nanoparticles in the cured binder composition may be:

• Greater than or equal to: 5 wt% or 6 wt% or 8 wt% or 10 wt%; and/or

• Less than or equal to: 35 wt% or 30 wt% or 25 wt% or 22 wt% or 20 wt% or 15 wt%.

Herein, the expression "mineral fibre product" includes any product which comprises bound mineral fibres, e.g. in the form of a sheet or a slab or any other desirable shape such as e.g. rolls, mats, felts, pipes etc, or just simple loose wool. Moreover, the present invention relates in a further aspect to a mineral fibre product obtainable by curing a mixture comprising mineral fibres and a binder composition.

The amount of mineral fibres in the mineral fibre product may be:

• Greater than or equal to: 80 wt% or 85 wt% or 90 wt% or 92 wt%; and/or · Less than or equal to: 99.5 wt% or 99 wt% or 98.5 wt% or 98 wt%.

The amount of cured binder in the mineral fibre product may be:

• Greater than or equal to: 0.5 wt% or 1 wt% or 1 .5 wt% or 2 wt%; and/or

• Less than or equal to: 15 wt% or 10 wt% or 8 wt% or 7 wt%.

A further aspect of the present invention relates to a use of nanoparticles in the manufacture of a mineral fibre product.

In a specific embodiment of the above-defined use, the nanoparticles are contained in the binder composition, or the nanoparticles are applied to the mineral fibres at any time before curing. The composition can be advantageously used as a binder in the production of nano- particle-reinforced mineral fibre products, such as products for acoustic or thermal insulation, wherein said binder results in improved mechanical properties. This positive effect is inter alia based on the presence of said nanoparticles, which promote the formation of the binder polymer, particularly at the crossing portions of the individual fibres, and further mechanically support said polymerized binder. As a consequence, the amount of binder in the final mineral fibre product may also be reduced while maintaining the above-mentioned desirable mechanical properties of the final product. Such a reduction of binder components and additives is advantageous both ecologically and economically.

In the following, the present invention will be further illustrated in the examples, however, without being limited thereto. Examples:

In each table set out in the examples, the LOI indicated is the LOI of Sample 1 (standard) of the table in question and the other samples in the same table were produced using the same volume and flow rate of binder solution as Sample 1 (stand- ard) of the table in question.

In the tables of mechanical properties the figures indicated in brackets after Cs and Tr are the minimum desired values for the properties. For example Cs(30) [kPa] indicates a minimum desired Cs value of 30 kPa for the product in question.

Example 1 :

Production of binder compositions and mineral wool products

Five different binder compositions (samples 1 to 5) were prepared according to the compositions provided in the following Table 1 . From these different sample compositions, samples 1 and 2 represent standard binder compositions which do not contain any nanoparticles. The resin used is phenol-formaldehyde, the nanoparticles used are S1O2 nanoparticles, the dust oil used is Garo 217S, and the silane used is aminosilane (from Momentive).

The such obtained binder compositions were used in the manufacture of a rock mineral wool product for fagade build application having a density of 125 kg/m³, an LOI (loss on ignition, herein determined according to EN 13820) of 3.5%.

The mechanical property-forecast for products obtained in two different testing sites (Lab 1 and Lab 2) is provided in Table 2. In this context, "forecast" means that the figures are already normalized to density variations and the deviation is also incorporated.

Table 1 :

In said mechanical property-forecast, compressive stress (Cs) and tensile resistance (Tr) were determined in accordance with EN826 and EN 1607, respectively, for a mineral fibre product in the dry product ("Dry"). Moreover, water repellency has been determined according to EN1609. As can be readily taken from Table 2, the mineral fibre products of samples 3 to 5 offer comparable or better mechanical properties in compressive stress, tensile resistance and or water repellency.

Example 2:

Production of binder compositions and mineral wool products

Three different binder compositions (samples 1 to 3) were prepared according to the compositions provided in the following Table 3. From these different sample compositions, sample 1 represents a standard binder composition which does not contain any nanoparticles. The resin used is phenol-formaldehyde, the nanoparticles used are S1O2 nanoparticles, and the dust oil used is Garo 217S. The such obtained binder compositions were used in the manufacture of a rock mineral wool product of insulation cores produces as lamellas having a density of 1 10 kg/m³, an LOI (loss on ignition, herein determined according to EN 13820) of 4.0%.

The mechanical property-forecast for products obtained in two different testing sites (Lab 1 and Lab 2) is provided in Table 4. In said mechanical property-forecast measurements, compressive stress (Cs), tensile resistance (Tr) and water repellency were determined as outlined in Example 1 .

Table 4 shows that the mineral fibre products of samples 2 and 3 are comparable or even superior in at least one of the determined properties of compressive stress, tensile resistance and water repellency, even though less resin, i.e. less binder components have been used therein. This clearly shows that the use of nanoparticles in a mineral fibre product can provide mechanical properties improved so much that the absolute amount of resin can be reduced without imparting the binder's characteris- tics.

Table 3: Recipes; Lamellas, 110 kg/m3, 4,0 % LOI

Table 4: Mechanical properties forecast

Example 3:

Production of binder compositions and mineral wool products

Five different binder compositions (samples 1 to 5) were prepared according to the compositions provided in the following Table 5. From these different sample compositions, sample 1 represents a standard binder composition which does not contain any nanopartides. The resin used is phenol-formaldehyde, the nanopartides used are: a combination of S1O2 and T1O2 nanopartides (nanopartidesi in sample 2), a mixture of emulsifying system with S1O2 nanopartides (nanoparticles2 in sample 3), T1O2 nanopartides (nanoparticles3 in sample 4), and S1O2 nanopartides in water (nanoparticles4 in sample 5). The dust oil used is Garo 217S.

The such obtained binder compositions were used in the manufacture of a rock mineral wool product for use at fagade insulation having a density of 1 10 kg/m³, an LOI (loss on ignition, herein determined according to EN 13820) of 3.5%. The mechanical properties for the products obtained in two different testing sites (Lab 1 and Lab 2) are provided in Table 6. In said mechanical property measurements, compressive stress (Cs), tensile resistance (Tr) and water repellency were deter- mined as outlined in Example 1 .

As can be derived from the experimental data given in Table 6, the mineral fibre products of samples 2 to 4 are comparable or even superior in at least one of the determined properties of compressive stress, tensile resistance and water repellency, even though significantly less resin, i.e. less phenol-formaldehyde binder components have been used therein. This clearly shows that the use of nanoparticles in a mineral fibre product can provide mechanical properties improved so much that the absolute amount of resin can be reduced without imparting the binder's characteristics.

Table 5:

Recipes; Facade boards,

110 kg/m3, 3,5 % LO

Sample 1 Sample 2 Sample 3 Sample 4 Sample 5

(standard) (nanoparticlesi ) (nanoparticles2) (nanoparticles3) (nanoparticles4)

Ingredients Amount Amount Amount Amount Amount

% % % % %

Resin 17.0 1 1 .0 1 1 .0 1 1 .0 1 1 .0

Water 82.3 88.5 88.5 88.5 88.5

Ammonia 0.07 0.07 0.07 0.07 0.07

Nanoparticles - 0.13 0.13 0.13 0.13

Dust oil emulsion 0.60 0.30 0.30 0.30 0.30

Table 6: Mechanical properties average

Dry Dry Dry Dry Dry

Cs (30) [kPa] 46.2 41.5 37.2 38.5 37.1

Lab 1

Tr (10) [kPa] 17.4 15.8 15.8 15.2 13.8

Cs (30) [kPa] 46.1 37.5 39.6 36.4 34.7

Lab 2

Tr (10) [kPa] 22.0 18.4 17.2 18 16

Water

<1 kg/m2 1.0 0.5 0.5 0.4 0.2 repellency Example 4:

Production of binder compositions and mineral wool products

Six different binder compositions (samples 1 to 6) were prepared according to the compositions provided in the following Table 7. From these different sample compositions, sample 1 represents a standard binder composition which does not contain any nanoparticles. The resin used is phenol-formaldehyde, the nanoparticles used are: a combination of S1O2 and T1O2 nanoparticles (nanoparticlesl in sample 5), a mixture of emulsifying system with S1O2 nanoparticles (nanoparticles2 in sample 6), T1O2 nanoparticles (nanoparticles3 in sample 3), and S1O2 nanoparticles in water (nanoparticles4 in sample 4). The dust oil used is Garo 217S, the silane used is ami- nosilane (from Momentive)

The such obtained binder compositions were used in the manufacture of a rock min- eral wool product for fagade insulation having a density of 153 kg/m³, an LOI (loss on ignition, herein determined according to EN 13820) of 3.5%.

The mechanical properties for the products obtained in two different testing sites (Lab 1 and Lab 2) are provided in Table 8. In said mechanical property measurements, compressive stress (Cs), tensile resistance (Tr) and water repellency were determined as outlined in Example 1 . Moreover, Cs and Tr were also determined after autoclave treatment, wherein the samples are exposed to high humidity and high temperature in an autoclave ("AC"), i.e. at 120 °C at a pressure of 2 bar for 20 minutes. It is particularly desirable if the compressive strength and/or tensile resistance following autoclave are at least 50% of the values prior to autoclave.

The experimental data of Table 8 clearly show that the mineral fibre products of samples 2 to 6 are comparable or even superior in at least one of the determined properties of compressive stress, tensile resistance and water repellency, even though significantly less of resin, oil and silane have been used therein. As a result, it is the use of nanoparticles in the binder composition allows not only to reduce the amount of resin but also to lower the amounts of other components without sacrificing the mechanical properties of the final mineral fibre product.

Table 7:

Receipts; Fascade boards, 153 kg/m3, 3,5 % LOI

Table 8:

Mechanical properties - average

Example 5:

Production of binder compositions and mineral wool products

Five different binder compositions (samples 1 to 5) were prepared according to the compositions provided in the following Table 9. From these different sample compositions, sample 1 represents a standard binder composition which does not contain any nanoparticles. The resin used is phenol-formaldehyde, the nanoparticles used are: a combination of S1O2 and T1O2 nanoparticles (nanoparticlesl in sample 2, 3 and 4), and a mixture of emulsifying system with S1O2 nanoparticles (nanoparticles2 in sample 5). The dust oil used is Hydrowax, and the silane used is aminosilane (from BRB).

The such obtained binder compositions were used in the manufacture of a rock mineral wool product used for fagade insulation having a density of 140 kg/m³, an LOI (loss on ignition, herein determined according to EN 13820) of 3.0%.

The mechanical properties for the products are provided in Table 10. In said mechanical property measurements, compressive stress (Cs), tensile resistance (Tr) and water repellency were determined as outlined in Example 1 .

The results presented in Table 10 show that the binder compositions used in samples 2 to 5 results in satisfactory mineral fibre product, despite that fact that the amount of resin is reduced to 10.0 or 9.4% solids, compared to 17% solids in the standard binder. It is particularly observed that the significant reduction of binder and oil in the binder compositions still results in mineral fibre products having advantageous mechanical properties. Table 9:

Receipts; Fascade boards; 140 kg/m3, 3,0 % LOI

Table 10:

Mechanical properties - average

Claims

A method of manufactunng a mineral wool insulation product comprising:

(a) applying a binder composition in the form of an aqueous binder solution and a dispersion of inorganic nanopartides to mineral fibres wherein the amount of nanopartides, based on the total weight of the aqueous binder composition, is in the range of 0.001 wt % to 35 wt %;

(b) collecting the mineral fibres to which the binder composition and the nanopartides have been applied to form a batt of mineral fibres; and

(c) curing the batt comprising the mineral fibres, the binder composition and the nanopartides to obtain a bound mineral fibre product.

The method of manufacturing a mineral wool insulation product according to claim 1 , wherein the amount of nanopartides, based on the total weight of the aqueous binder composition, is in the range of 0.01 wt % to 5 wt %, notably in the range of 0.1 wt % to 3 wt %.

The method of manufacturing a mineral wool insulation product according to claim 1 , wherein the amount of nanopartides, based on the total weight of the aqueous binder composition, is in the range of 0.05 wt % to 1 wt %.

The method of manufacturing a mineral wool insulation product according to claim 1 , wherein the amount of nanopartides, based on the total weight of the aqueous binder composition, is greater than 5% and less than or equal to 35%.

The method of manufacturing a mineral wool insulation product according to any preceding claim comprising mixing the aqueous binder solution and the dispersion of nanopartides and subsequently applying the mixed aqueous binder solution and dispersion of nanopartides to the mineral fibres.

The method of manufacturing a mineral wool insulation product according to any preceding claim wherein the mineral fibres are selected from stone wool fi- bres and glass wool fibres.

The method of manufacturing a mineral wool insulation product according to any preceding claim wherein the one or more curable binder components are selected from the group consisting of (i) phenol-formaldehyde, (ii) phenol- melamine, (iii) urea-formaldehyde, (iv) polyvinyl acetate (PVA), (v) reducing sugars and (vi) reaction products of at least one carbohydrate component and at least one amine component.

The method of manufacturing a mineral wool insulation product according to any preceding claim wherein the nanoparticles comprise one or more compounds selected from the group consisting of metal oxides and inorganic nano- tubes.

The method of manufacturing a mineral wool insulation product according to any preceding claim wherein the nanoparticles comprise one or more compounds selected from the group consisting of S1O2, T1O2, MgO, AI2O3, MnO, CuO, AgO and clay.

The method of manufacturing a mineral wool insulation product according to any preceding claim wherein the binder composition further comprises at least one dust oil or dust oil emulsion.

The method of manufacturing a mineral wool insulation product according to any preceding claim wherein the binder composition further comprises at least one silane.

12. A mineral wool insulation material comprising mineral fibres held together by a cured binder, characterized in that the binder comprises inorganic nanoparticles present in an amount of 0.01 to 35 wt % with respect to the total dry weight of the cured binder.

13. The mineral wool insulation material according to claim 12, wherein the nano- particles are present in an amount of 0.01 to 5 wt % with respect to the total dry weight of the cured binder, notably in an amount of 0.05 wt % to 2 wt % with respect to the total dry weight of the cured binder.

14. The mineral wool insulation material according to claim 13, wherein the nano- particles are present in an amount of greater than 5 wt % to less than or equal to 35 wt % with respect to the total dry weight of the cured binder.

15. The mineral wool insulation material according to claim 13 or claim 14, wherein mineral fibres are selected from stone wool fibres and glass wool fibres.