Vegetable oil-based o / w formulations

Abstract

A vegetable oil-based formulation which is an oil in water (O / W) emulsion comprising at least one refined vegetable oil with a flash point higher than 260ºC; at least one anionic surfactant, at least one non-ionic surfactant or a combination thereof; at least one rheological additive which is an ionic polysaccharide; and water; wherein the formulation has an active matter content of about 31 wt% and about 69 wt% and the rest of the formulation, until reaching 100 wt.%, is water; and wherein the viscosity of the formulation is of about 100 cP to about 1500 cP (25ºC, Viscosimeter Brookfield HV, 20 rpm). A method of manufacturing said formulation and uses thereof.

Description

[0001] VEGETABLE OIL-BASED O / W FORMULATIONS

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to vegetable oil-based O / W formulations, an environmentally friendly alternative to formulations based on mineral oil, which are obtainable from renewable resources instead of non-renewable resources. They comprise an O / W emulsion that contains refined vegetable oils with a flash point higher than 260°C and water, as well as specific surfactants and rheological additives which in combination result in a kinetically stable emulsion and formulation.

[0004] The vegetable oil-based formulations of the invention are kinetically stable and particularly useful for controlling dust typically generated in manufacturing, handling or installing fibre insulation products. More specifically, the invention provides an antidusting formulation for manufacturing fibreglass, rock wool or slag wool insulation products, so that the amount of dust generated during the manufacturing, handling or installing of those products can be significantly reduced.

[0005] These formulations can also be used for other applications such as increasing the flexibility of polyflavonoid-based foams (i.e., tannin-based foams), or improving the release of boards from the molds used during manufacture, for example, but not limited to, of wood derived boards, fibreboards (including MDF and HDF boards, i.e., mediumdensity and high-density fibreboards), particleboards, chip boards, oriented strand boards, plywood, paperboards, and boards or insulations made from fibreglass, rock wool or slag wool.

[0006] The invention also refers to articles treated or manufactured with the formulations of the invention, for example the insulation products, panels, foams or boards obtained by the use of said formulations.

[0007] BACKGROUND OF THE INVENTION

[0008] Different types of mineral fibres including fibreglass, rock wool, slag wool and the like are being used extensively in the manufacturing of thermal or acoustical insulation products.

[0009] The manufacture of said insulation products generally comprises a step of preparing the mineral fibres themselves, which can be performed by different procedures, for example according to the techniques known as rotary process (internal centrifuge), cascade process (external centrifuge), and flame attenuation process (pot & marble). To ensure the assembly and adhesion of the fibres, an adhesive resin, generally a thermosetting resin, is projected onto the fibres (glass fibre, rock wool or slag wool) or mixed with them. The mixture of fibres and resin is subjected to a thermal treatment, at a temperature generally higher than 150 °C, such as around 200 °C, for the polycondensation of the resin to take place and thus obtain a thermal and / or acoustic insulation product. Commonly used adhesive compositions are, for example, acid or basic phenolic resins, sugar-based resins or starch-based resins.

[0010] However, it is known in the art that there is a serious problem associated with these insulation products since a great amount of dust may be generated in manufacturing, handling or installing them, and said dust can cause different harmful health effects in people involved on these activities and / or residents in a large area around the manufacturing plant. These effects on health may be, for example, irritation of the skin, eyes, nose or throat or, in some cases, they may derive in severe respiratory or dermatological disorders.

[0011] Mineral oils, in particular bright stock oils, have been extensively used as anti-dusting agents in the manufacture of the above-mentioned insulation products. However, they are based on non-renewable resources, cause environmental problems (e.g., air pollution) and, when mixed with the adhesive composition, tent to result in a rapid separation of phases despite the use of stirring mechanisms.

[0012] Some attempts have been made to overcome the above-mentioned drawbacks associated with the use of mineral oil as anti-dusting agent. Thus, for example, US 3,861 ,895 discloses a composition wherein mineral oil is replaced by a polyalkene glycol component with the aim to avoid air pollution, whereas patent applications W095 / 06013 A1 and W02009 / 046521 A1 refer to the incompatibility of mineral oils with the adhesive composition comprising the resin. More specifically, W095 / 06013 A1 discloses the combination of mineral oil with an unspecified emulsifier prior mixing with the adhesive composition. The mixture comprising the emulsified oil and the adhesive composition is stable during the application step through the nozzles, but there is no indication or suggestion in this patent application that such formulation can be pre-mixed and stored prior to the application step. On the other hand, W02009 / 046521 A1 provides an aqueous anti-dusting emulsion formulation for use in the manufacture of fibre wool insulation, wherein the formulation may comprise a petroleum hydrocarbon, a triglyceride and a surfactant. Some of the embodiments disclosed therein, however, do not comprise the petroleum hydrocarbon component. According to this patent application, the petroleum hydrocarbon component may be mineral oil, bright stock oil, paraffinic slack wax or petrolatum. The triglyceride may be palm oil, palm kernel oil, coconut oil, peanut oil, soybean oil, soy stearin, linseed oil, stearin oil, corn oil, cottonseed oil, rape seed oil, canola oil, sunflower oil, safflower oil, tung oil, castor oil, fish oil, lard, tallow, tall oil, animal fats and mixtures thereof. And the surfactant comprises a sodium or ammonium salt of a lignosulphonic acid. In particular, W02009 / 046521 A1 discloses an anti-dusting emulsion formulation (sample 2) obtained by adding unmodified soy oil to a water solution comprising ammonium lignosulphonate under a high-speed mixer, followed by homogenization at 3000 psi, and then cooling to ambient temperature. According to the experimental data provided by this patent application, no separation was observed in sample 2 after 1 hour. Inventors of the present invention found, however, that the emulsion identified as sample 2 in W02009 / 046521 A1 (also referred to as Walker's emulsion E2 in this document) shows a non-gaussian distribution with a Sauter mean diameter (D(3,2)) of 0.1 pm and a stability at normal conditions of less than 24 hours (see figure 3 below).

[0013] DESCRIPTION OF THE INVENTION

[0014] It is an object of the present invention to obtain O / W emulsion formulations by using a vegetable-based product as the main raw material, i.e., formulations based on dispersing refined vegetable oils, in particular refined soybean oil, in a water phase.

[0015] These raw materials help reduce the dependency on mineral oil (petroleum), reduce the carbon footprint and avoid the price swings of raw materials indexed to oil prices. Mineral oil conventionally used as anti-dusting in the isolation industry is a non-renewable resource, whereas vegetable oils are a renewable resource; therefore, vegetable oilbased formulations are environmentally friendly.

[0016] One problem to be solved by the present invention thus is to provide an environmentally friendly alternative to formulations based on mineral oil, which are obtainable from renewable resources instead of non-renewable resources. This is solved by the kinetically stable vegetable oil-based formulations according to the invention, which are O / W emulsions comprising refined vegetable oils with a flash point higher than 260 °C, low levels of specific surfactants and rheological additives, and water. Said formulations can be manufactured on an industrial level, and completely or partially avoid the use of non-renewable resources, e.g., petroleum derived resources such as mineral oils. Due to their particular composition, viscosity and, preferably, particle size distribution, the formulations of the invention have a high kinetic stability (at least 1 month at normal conditions). Said formulations are particularly useful for controlling dust generated in manufacturing, handling or installing fibre insulation products and, therefore, they can be used as anti-dusting agents in the manufacture of said articles, in particular fibreglass, rock wool or slag wool insulation products.

[0017] These vegetable oil-based formulations can also be used for other applications such as increasing the flexibility of polyflavonoid-based foams, or improving the release of boards from the molds used during manufacture, for example, but not limited to, of wood derived boards, fibreboards (including MDF and HDF boards, i.e., medium-density and high- density fibreboards), particleboards, chip boards, oriented strand boards, plywood, paperboards, and boards or insulations made from fibreglass, rock wool or slag wool.

[0018] Thus, an object of the invention is a vegetable oil-based formulation which is an oil in water (O / W) emulsion comprising:

[0019] - about 30 wt.% to about 60 wt.% of at least one refined vegetable oil with a flash point higher than 260°C, preferably higher than 280°C, measured according to ASTM D92-18;

[0020] - about 1 wt.% to about 5 wt.% of at least one anionic surfactant, at least one nonionic surfactant or a combination thereof, wherein

[0021] - the anionic surfactant is selected from aryl sulfonate, >Ci2 alkyl sulfate, >Ci2 alkyl carboxylate, alkaline salt of C10-C15 alkyl-aryl sulfonic acid and a combination thereof, and

[0022] - the non-ionic surfactant is selected from primary alcohol ethoxylate, secondary alcohol ethoxylate and a combination thereof, wherein said non-ionic surfactant has a HLB higher than 8;

[0023] - about 0.2 wt.% to about 4 wt.% of at least one rheological additive which is an ionic polysaccharide, preferably selected from the group consisting of gum ghatti, xanthan gum and a combination thereof; and

[0024] - water; wherein the formulation has an active matter content of about 31 wt% and about 69 wt% and the rest of the formulation, until reaching 100 wt%, is water, the active matter content comprising all the components which are different from water; and wherein the viscosity of the formulation is of about 100 cP to about 1500 cP, preferably 150 cP to 1200 cP (25°C, Viscosimeter Brookfield HV, 20 rpm, preferably spindle 02).

[0025] The formulation of the invention is particularly useful for the intended uses, especially for controlling dust typically generated in manufacturing, handling or installing fibre insulation products, since it complies with the following features: 1. High active matter content: about 31 wt.% to about 69 wt. %, preferably about 45 wt.% to about 55 wt. %.

[0026] 2. High stability: at least 1 month (kinetic stability), preferably at least 2 months, more preferably at least 6 months, and even more preferably at least 12 months, at normal conditions of temperature and pressure.

[0027] 3. Suitable performance as anti-dusting agent, so that the generation of dust can be significantly reduced when an insulation product is manufactured with the formulation of the invention (see further details in the Examples section below).

[0028] 4. Good compatibility with adhesive resins conventionally used in the manufacture of insulation product, in particular acid or basic phenolic resins, sugar-based resins or starch-based resins.

[0029] Viscosity ranges and values specified in this document are expressed in cP, a well- known viscosity unit commonly used in the technical field of the invention. These viscosity ranges and values can be unambiguously converted to the corresponding ranges and values according to SI Units (Pa s), since that 1 cP is equal to 10'3Pa s. For instance, the emulsion of the invention has a preferred viscosity of 150 cP to 1200 cP, i.e., of 0.15 Pa s to 1.2 Pa s. The viscosity can be measured at 25°C using a Brookfield HV Viscometer, in particular DV-1 , preferably spindle 02, at 20 rpm.

[0030] An emulsion, according to the IUPAC, is a “fluid colloidal system in which liquid droplets and / or liquid crystals are dispersed in a liquid. The droplets often exceed the usual limits for colloids in size. An emulsion is denoted by the symbol O / W if the continuous phase is an aqueous solution and by W / O if the continuous phase is an organic liquid (an 'oil'). More complicated emulsions such as O / W / O (i.e., oil droplets contained within aqueous droplets dispersed in a continuous oil phase) are also possible.”

[0031] On the other hand, a suspension, according to the IUPAC, is “a liquid in which solid particles are dispersed”.

[0032] Vegetable oils comprised in the formulation of the invention are liquids at normal temperature and pressure conditions (i.e., at a temperature of 20°C and an absolute pressure of 1 atm (101 MPa)) and, therefore, they form O / W emulsions.

[0033] Waxes are generally considered to be mixtures of esters with high molecular masses formed by fatty acids and monohydroxylated alcohol, wherein n and m represent the number of times the CH2 group is repeated. As such, the most frequent values are: n = 8-18 and m = 16-36.

[0034] (general structure of a wax)

[0035] Glycerides are made up of fatty acids with a high molecular mass and trihydroxylated alcohols such as propanetriol, glycerol or glycerine.

[0036] Glycerides can have an esterified hydroxyl group, called monoglyceride, diglyceride when they have two esterified hydroxyl groups, and triglyceride when three hydroxyl groups were esterified.

[0037] When glycerides have saturated carbon chains, they are referred to as fats, all the carbon atoms exhibit sp3 hybridisation, except the carbon of the functional group (ester), from which it can be deduced that the fatty acids in these structures are saturate chains.

[0038] In general, vegetable oils are characterised by the presence of double bonds in the fatty acid chains that form the glyceride structure, and therefore not all the carbon atoms exhibit sp3 hybridisation, a new functionality appears, where the carbon atoms exhibit sp2 hybridisation and different chemical reactivity, and the fatty acids present are not saturated. Note that the saturated fatty acids have a specific packing or order in the triglyceride molecules, which explains why the fats are solid substances, whereas the particular stereochemistry of the fatty acids that make up the oils (unsaturated fatty acids) with geometric isomers, the most abundant being cis isomer, provides a different spatial order, which can be seen in the figures below.

[0039] (May be in solid state at normal conditions)

[0040] (May not be in solid state at normal conditions)

[0041] In the frame of the present invention, it should be understood that the expression “refined vegetable oils” refers to crude oils obtained by mechanical or solvent extraction of vegetables, which have been chemically or physically refined to get a better quality, a more acceptable aspect (limpidity), a lighter odour and colour, longer stability and good safety through the elimination of pollutants. Refined vegetable oils may be obtained by conventional processes as those described, for example, in Said Gharbi, The Scientific World Journal, Vol. 2022, Article ID 6627013 (2022). Those refined vegetable oils have not been subjected to any kind of hydrogenation and, therefore, they can also be referred to as non-hydrogenated oils or non-hydrogenated vegetable oils.

[0042] Refined vegetable oils comprised in the formulation of the invention are characterized by having a flash point higher than 260°C, preferably higher than 280°C, so that they can be used in the manufacturing of insulation products. Said high flash point is important in order to avoid fire in the manufacturing process of insulation product, which typically requires thermal treatment at temperatures higher than 150 °C, typically around 200°C.

[0043] In the frame of this invention, it should be understood that the term “flash point” refers to the lowest temperature, measured to a barometric pressure of 101.3 kPa, at which application of an ignition source causes the vapour of the test portion to ignite momentarily and the flame to propagate across the surface of the liquid under the specified conditions of test. The flash point may be determined following ASTM D92-18, Standard Test Method for Flash and Fire Points by Cleveland Open Cup Tester.

[0044] The refined vegetable oil is preferably selected from the group consisting of refined soybean oil, refined sunflower oil, refined rapeseed oil, refined corn oil, refined palm oil and mixtures thereof; more preferably refined soybean oil. The flash point of the at least one refined vegetable oil comprised in the formulation of the invention, preferably as defined in the previous paragraph, is higher than 260°C, preferably higher than 280°C, more preferably of 300°C to 350°C and, even more preferably of 310°C to 330°C.

[0045] The at least one vegetable oil comprised in the formulation described herein is a nonhydrogenated oil (i.e. , it comprises a high proportion of unsaturated fatty acids) which is liquid in normal conditions (20 °C and 1 atm (101 MPa)). Thus, said refined vegetable oil preferably has an iodine value higher of about 50 g iodine per 100 g of oil. The iodine value may be determined following the standard LINE-EN ISO 3961 :2018 Animal and vegetable fats and oils. Determination of iodine value.

[0046] According to some embodiments, the iodine value of the at least one refined vegetable oil having a flash point higher than 260°C as defined in this document, may be as follows:

[0047] In some particular embodiments, the vegetable oil is refined soybean oil having a flash point higher than 260°C, preferably higher than 280°C, more preferably of about 300 °C to about 350°C, even more preferably of about 310 °C to about 330°C, wherein its iodine value preferably ranges from about 120 g to about 155 g iodine per 100 g of soy oil, both parameters measured as defined in this document.

[0048] The amount of vegetable oil in the formulation of the invention ranges from about 30 wt.% to about 60 wt.% of the total weight of the formulation. In preferred embodiments, this amount may range from about 40 wt.% to about 60 wt.%, more preferably from about 45 wt.% to about 55 wt.%, of the total weight of the formulation. A lower content of vegetable oil would negatively affect dusting properties of the formulation. This reduced efficacy could be partially overcome by using a higher amount of formulation. However, this approach is not a suitable solution because it would result in a higher cost and, due to the low viscosity of the vegetable oil formulation thus obtained, said formulation is not stable over time, in particular, formulations having a vegetable oil content lower than 30 wt.% of the total weight of the emulsion are kinetically stable for less than 24 hours, at normal pressure and temperature conditions. A content of vegetable oil higher than 60 wt.% of the total weight of the emulsion also gives rise to formulations or emulsions having a reduced kinetic stability, since their viscosity is too high and, additionally, it is difficult to obtain the required particle size and distribution.

[0049] Oils have the difficulty that they have the property of occluding water inside their structure, normally between 2 and 6 times their weight. This property causes their emulsification to be very complicated, as it leads to the forming of semisolid creams, which makes it impossible to be properly applied to any material, e.g., by spraying, which is the preferred way of application, for which the product needs to be in a liquid state.

[0050] Emulsifiers are a group of substances of different origin and properties that may contribute to obtain a greater stabilization of the emulsions or suspensions; this is due mainly to its amphiphilic or double affinity character, which, from the physico-chemical point of view, is defined as a double polar and apolar property. Within this large group of compounds, we can find e.g., surfactants.

[0051] In the frame of this invention, it should be understood that the term “surfactant” (surfaceactive agent) refers to a substance that possesses superficial or interfacial activity. Surfactants are usually organic compounds that are akin to amphiphilic, which means that this molecule, being as double-agent, each contains a hydrophilic "water-seeking" group (the head), and a hydrophobic "water-avoiding" group (the tail). As a result, a surfactant contains both a water-soluble component and a water-insoluble component. Surfactants diffuse in water and get adsorbed at interfaces between air and water, or at the interface between oil and water in the case where water is mixed with oil. The waterinsoluble hydrophobic group may extend out of the bulk water phase into a non-water phase such as air or oil phase, while the water-soluble head group remains bound in the water phase. It should be noted that not all amphiphilic compounds possess such activity, so that it is required that the substance has relatively balanced properties, i.e., it must be neither too hydrophilic nor too hydrophobic.

[0052] The word "surfactant" does not have an exact translation in Spanish, where the generic term "tensioactivo" is used, which refers to an activity or an action on the surface or interfacial tension, i.e., on the Gibbs free energy. This term is equivalent to surfactant only if it is assumed that the surface or interfacial activity necessarily results in a decrease in tension, which is true in most cases of practical interest. The formulation of the invention comprises about 1 wt.% to about 5 wt.%, preferably about 1.5 wt.% to about 3 wt.%, of at least one anionic surfactant, at least one non-ionic surfactant or a combination thereof, wherein the anionic surfactant is selected from aryl sulfonate, (higher than C12) alkyl sulfate, (equal to or higher than C12) alkyl carboxylate, alkaline salt of C10-C15 alkyl-aryl sulfonic acid and a combination thereof, and the nonionic surfactant is selected from primary alcohol ethoxylate, secondary alcohol ethoxylate and a combination thereof, wherein said surfactant has a hydrophilic lipophilic balance (HLB) higher than 8.

[0053] These surfactants in combination with the rheological additive as described in this document are particularly useful in providing the kinetically stable O / W emulsion in the formulation of the invention. For instance, sulfate or carboxylate surfactants having an alkyl moiety lower than C12 typically generate a high amount of foam, which jeopardize the stability of the emulsion.

[0054] The term “kinetically stable” in the frame of the present invention means that the viscosity of formulations and emulsions to which the term refers to does not significantly change and, additionally, said formulations or emulsions do not separate into distinct phases within the indicated timeframe, for example, at least 1 months, preferably at least 2 months, more preferably at least 6 months, and even more preferably at least 12 months. Depending on the viscosity of a freshly prepared formulation or emulsion according to the invention, the allowed viscosity variation until it is considered that said formulation has lost its kinetically stability may be different. Thus, freshly prepared formulations having a viscosity value of 100 cP to 500 cP are deemed to become kinetically unstable when the viscosity doubles its value; whereas freshly prepared formulations having a viscosity value higher than 500 cP to 1000 cP are deemed to become kinetically unstable when the viscosity increases equal to or higher than 50 % of the initial value; and freshly prepared formulations having a viscosity value higher than 1000 cP are deemed to become kinetically unstable when the viscosity increases equal to or higher than 25 % of the initial value, provided that said viscosity is maintained equal to or lower than about 1500 cP; wherein viscosities are measured at 25°C, with a Viscosimeter Brookfield HV, 20 rpm, preferably spindle 02.

[0055] Phase separation can be visually tested in a 100 ml test-tube. Formulations and emulsions are considered not stable if the % volume of phase separation is higher than 5 % of the total volume of the sample.

[0056] “Non-ionic surfactants” are surfactants that do not bear an electrical charge in aqueous solution since their hydrophilic groups are of the alcohol, phenol, ether o amide type. A high proportion of these surfactants can be rendered relatively hydrophilic by the presence of a polyether chain of the polyethylene oxide type. Among those, alcohol ethoxylates are a class of non-ionic surfactants that contain a hydrophobic alkyl chain attached via an ether linkage to a hydrophilic ethylene oxide (EO) chain and have the general structure R(OCH2CH2)nOH, wherein R is the hydrophobic alkyl chain. Non- anionic surfactant that can be comprised in the formulation of the invention is selected from primary alcohol ethoxylate, secondary alcohol ethoxylate and a combination thereof, wherein said surfactant has a hydrophilic lipophilic balance (HLB) higher than 8, preferably higher than 10, more preferably of 12 to 14. Suitable non-ionic surfactants may be, for example, Tergitol® 15 S-9 (i.e., a secondary alcohol ethoxylate having a HLB of 12 to 14, and an EO content of 9), which is commercially available by Dow.

[0057] “Anionic surfactants” are surfactants that may be dissociated into an amphiphilic anion and a cation, usually an alkali metal or a quaternary ammonium. Anionic surfactant comprised in the formulation of the invention is selected from aryl sulfonate, (higher than C12) alkyl sulfate, (equal to or higher than C12) alkyl carboxylate, alkaline salt of C10-C15 alkyl-aryl-sulfonic acid and a combination thereof. Unless otherwise specified, said surfactants may be, in particular, alkaline or ethanolamine salts of the corresponding sulfonate, sulfate or carboxylate (fatty acid). Among those, aryl sulfonates, in particular naphthalene sulfonates such as sodium naphthalene sulfonate, are preferred because they are able to provide a high stability to the O / W emulsion over time (at least 6 months, preferably at least 12 months, at normal conditions), result in a stable vegetable oil-based formulation since the compatibility with other ingredients such as phenolic resins to be used as adhesive is higher in comparison to other surfactants, typically have a lower cost than alcohol ethoxylate and, additionally, they show a higher stability than sulfates and carboxylates in hard waters and pH changes.

[0058] Surfactants may either be added to the water or the oil phase. Alternative, if the surfactant comprises a salt of a fatty acid, it may be obtained in situ, within the water phase, by a saponification reaction. The weight percentages indicated refer to the final concentration of surfactants within the O / W emulsion formulation, independently of whether they were added as such or generated in situ by reaction of the fatty acids contained in the oils or waxes and an alkali, preferably an ethanolamine, which is added to the aqueous phase, before carrying out the emulsification. When adding the aqueous phase to the oil phase, or vice versa, the base will react with fatty acids of the oil phase and generate a surfactant in situ. The ethanolamine may be selected for example, but not limited to, from monoethanolamine, diethanolamine and triethanolamine. In the formulation of the invention, the ratio of surfactant vs. total amount of oil, generally known as S / O ratio, preferably is of about 1 wt.% to about 10 wt.%, more preferably of about 2 wt.% to about 8 wt.%, even more preferably of about 3 wt.% to about 5 wt.%.

[0059] Inventors found that O / W emulsions comprising refined vegetable oils, in particular those comprising refined soybean oil, tent to separate into phases when they are not formulated with the proper surfactant or do not have the correct viscosity. The present invention solves this problem by combining the required amount of specific surfactants as described herein with a very specific kind of rheological additives, i.e., an ionic polysaccharide such as gum ghatti, xanthan gum or mixtures thereof.

[0060] Rheology is the study of the principles that regulate the movement of fluids, i.e., substances that deform continuously when any kind of shear stress is applied to them. This branch of physics also studies the viscosity, elasticity, plasticity and spilling of fluids. Rheology modifiers have the ability to modify the rheological characteristics of both aqueous and non-aqueous formulations. Among those, polysaccharide-type rheology modifiers typically have a high molecular weight, are colourless, tasteless and have the property of being hydrocolloid, whereby they retain water and swell, resulting in an increase in viscosity. It is worth noting that not all rheology modifiers are suitable to overcome the technical problem posed above. Thus, some of them increase the viscosity too much, which makes the use of the emulsion unfeasible in certain situations, whereas other additives may be incompatible with the resins used in the manufacturing of insulation products.

[0061] The vegetable oil-based formulation of the invention comprises about 0.2 wt.% to about 4 wt.%, preferably about 0.5 wt.% to about 1 .5 wt.%, of at least one rheological additive which is an ionic polysaccharide, preferably selected from the group consisting of gum ghatti, xanthan gum and a combination thereof, more preferably gum ghatti.

[0062] Gum ghatti (CAS Number 9000-28-6) is a complex polysaccharide gum of high molecular weight which may be extracted from Anogeissus latifolia, a tree originates from India. This ionic polysaccharide is mainly composed of the calcium and magnesium salts of L- arabinose, D-galactose, D-manose, D-xylose, D-glucuronic acids, in particular, in the approximate molar ratio of 10:6:2:1 :2. Typically, gum ghatti disperses in cold water forming viscous solutions at concentrations of about equal to or higher than 5 wt.%, which show a no-Newtonian behavior. A maximum viscosity is achieved at a concentration between 5 wt.% and 7 wt.%.

[0063] Xanthan gum (CAS Number 11138-66-2) is a polysaccharide gum that can be produced from simple sugars using a fermentation process with bacteria from the specifies Xanthomonas campestris. The primary structure of this ionic polysaccharide is mainly composed of D-glucose and D-mannose along with D-glucuronic acid.

[0064] The vegetable oil-based formulation of the invention comprises about 31 wt.% to about 69 wt.% of active matter content. According to some embodiments the active matter content is of about 45 wt.% to about 55 wt.%. The active matter content refers to the total weight of the sum of all the components of the formulation which are different from water.

[0065] Due to the specific combination of surfactant and rheological additive described herein, the formulation of the invention has a viscosity of about 100 cP to about 1500 cP, preferably about 150 cP to about 1200 cP, more preferably of about 300 cP to about 600 cP. The viscosity can be measured at 25°C using a Brookfield HV Viscometer, in particular DV-1 , preferably spindle 02, at 20 rpm.

[0066] In some preferred embodiments, the vegetable oil-based formulation of the invention is also characterized in that the oil particles in the emulsion have a gaussian distribution with a Sauter mean diameter (D(3,2)) of about 0.5 pm to about 1.5 pm, preferably of about 0.5 pm to about 1.0 pm, measured by laser diffraction in a Mastersizer 300 equipment.

[0067] “Sauter mean diameter”, also designated as D(3,2), D32 or D(32) is the mean diameter with the same ratio of volume to surface area as the entire ensemble. It was originally developed by German scientist Josef Sauter in the late 1920s. The size of drops is determined based on the absorption / scattering of light. The technique depends on the fact that absorption / scattering is proportional to the surface area of the drops.

[0068] The small size and gaussian distribution of the oil particles in the O / W emulsion of the invention help to increase the stability of the emulsion and, at the same time, improve the effectivity of the vegetable oil-based formulation for controlling dust since the oil drops can be more effectively distributed in the fibre.

[0069] The formulation of the invention preferably has a density of about 0.94 g / m3to about 0.98 g / m3, measured by pycnometer according to the standard ISO 2811-1 :2023.

[0070] The vegetable oil-based formulations according to the invention are kinetically stable, which means that they do not significantly change its viscosity nor separate into distinct phases within the indicated timeframe, e.g., no oil particles appear throughout the formulation within a time frame. According to some embodiments, the formulation of the invention is kinetically stable during at least 1 months at normal temperature and pressure conditions, preferably at least 2 months, more preferably at least 4 months, still more preferably at least 6 months, even more preferably at least 1 year, and the most preferably at least 2 years. This stability allows the formulation to be commercially distributed and offered, without the need of special conditions or equipment.

[0071] The timeframe of kinetical stability may be even further increased, to at least two years, by reducing the storing temperature, e.g., to temperatures lying between 5°C and 15°C, preferably between 5°C and 10°C.

[0072] In addition to the surfactants and rheological additives as described in this document, the vegetable oil-based formulation of the invention may comprise other additives such as, for example, biocides which may be added to the formulation with the aim avoid the development of mildew, since it may negatively affect the applicability of the vegetable oil-based formulation of the invention. In particular embodiments of the invention, said biocide may be present in the vegetable oil-based formulation of the invention in an amount of about 0.05 wt.% to about 0.3 wt.%, in particular, in an amount of 0.1 wt.% with respect to the total weight of the formulation. Suitable biocides commercially available that can be used are, for example, Mergal® 758, Acticide® MBS, Mirecide® M 1 85.

[0073] The vegetable oil-based formulation according to the invention may be obtained by different methods of emulsification, including methods of emulsification well known in the art. For example, said O / W emulsion formulation may be obtained by direct emulsification method (sometimes herein referred to as direct O / W method), by slowly adding the oil phase to the water phase, both heated to temperatures equal to or higher than 70°C, preferably of about 70 °C to about 80 °C, under stirring or equivalent means of mixing. The surfactant may be contained either in the oil phase or the water phase, normally, but not necessarily, an ionic surfactant is added to the water phase, and a nonionic surfactant to the oil phase. Alternatively, the surfactant may be obtained in situ by reaction of corresponding reagents.

[0074] Thus, the invention also provides a method of manufacturing a vegetable oil-based formulation as described in this document, wherein the method comprises: a) obtaining a water phase comprising a rheological additive which is an ionic polysaccharide preferably selected from the group consisting of gum ghatti, xanthan gum and a combination thereof and, optionally, at least one anionic or non-ionic surfactant as defined in this document; b) obtaining an oil phase comprising at least one refined vegetable oil with a flash point higher than 260°C and, optionally, at least one anionic or non-ionic surfactant as defined in this document; wherein at least one of the water phase or the oil phase comprises at least one surfactant as defined above; c) heating the water phase and the oil phase at a temperature equal to or higher than about 70°C, preferably of about 70 to about 80°C; d) adding the heated oil phase to the heated water phase and stirring the mixture at a temperature equal to or higher than about 70°C, preferably of about 70°C to about 80°C, for at least 20 minutes; e) homogenizing the mixture of step d); and f) gradually cooling the homogenized mixture of step e) until a temperature of 20°C to 30°C, preferably of 20°C to 25°C; wherein the surfactant, rheological additive, refined vegetable oil and water are added in such an amount to obtain a formulation as defined herein.

[0075] All ingredients of the formulation are as described in this document. In particular, the refined vegetable oil may be selected from the group consisting of refined soybean oil, refined sunflower oil, refined rapeseed oil, refined corn oil, refined palm oil and mixtures thereof; and the surfactant may be selected from aryl sulfonates, fatty acid salts, alcohol ethoxylates and mixtures thereof.

[0076] In particular embodiments of the method of the invention, the formulation comprises at least one anionic surfactant selected from aryl sulfonate, >Ci2 alkyl sulfate, >Ci2 alkyl carboxylate, alkaline salt of C10-C15 alkyl-aryl-sulfonic acid and a combination thereof, preferably an aryl sulfonate surfactant, preferably a naphthalene sulfonate surfactant, more preferably sodium naphthalene sulfonate; and said anionic surfactant is comprised in the aqueous phase obtained in step a). However, anionic surfactants as described in this document can also be present in the oil phase obtained in step b), since the pre-mix time of step d) (at least 20 minutes) is enough to solubilize them.

[0077] In particular embodiments of the method of the invention, the formulation comprises at least one non-ionic surfactant selected from primary alcohol ethoxylate, secondary alcohol ethoxylate and a combination thereof, wherein said non-ionic surfactant have a HLB higher than 8, preferably a HLB higher than 10, more preferably of 12 to 14; and said non-ionic surfactant is comprised in the oil phase obtained in step b). However, non- ionic surfactants as described in this document can also be present in the aqueous phase obtained in step a), since the pre-mix time of step d) (at least 20 minutes) is enough to solubilize them. In some embodiments, the oil phase can be added to the water phase in a period of time of about 10 minutes to about 40 minutes, preferably of about 15 minutes to 30 minutes, the mixture obtained by addition of the heated oil phase to the heated water phase in step d) can be stirred at a rate of 30 rpm to 350 rpm for at least 20 minutes; the homogenization of step e) can be carried out in an homogenizer at a pressure of about 30 bar (3 MPa) to about 350 bar (35 MPa) preferably for a period of 1 min to 30 min; and / or the homogenized mixture can be gradually cold at a rate of 1 to 7 °C / min in step f), preferably of 4 to 7 °C / min.

[0078] The homogenization step, in particular when it is carried out in an homogenizer at a pressure of about 30 bar (3 MPa) to about 350 bar (35 MPa), preferably for a period of 1 min to 30 min, allows the generation of the oil particles in the emulsion have a gaussian distribution with a Sauter mean diameter (D(3,2)) of about 0.5 pm to about 1.5 pm, preferably of about 0.5 pm to about 1.0 pm, measured by laser diffraction in a Mastersizer 300 equipment.

[0079] For the same emulsification conditions given, the particle diameter is inversely proportional to the applied pressure. The homogenization may be carried out using a two-stage homogenizing valve assembly, also referred to as two-phase homogenizer in this document, which includes a first-stage valve and a second-stage valve that serves to exert a backpressure of the fluid moving through the first-stage valve. According to these embodiments, the homogenization is carried out in two different homogenization sub-stages or phases, wherein different pressures are applied in each of these substages, in order to further reduce the particle diameter. Typically, pressure applied in the second homogenization sub-stage (i.e. , pressure applied to the second-stage valve) is of about 10% to about 20% of the pressure of the first homogenization sub-stage.

[0080] On the other hand, the emulsification according to the method of the invention may be carried out either in a single reactor, by using mechanical dispersion, a rotor-stator, or with stirring and homogenizer.

[0081] Alternatively, the emulsification according to the invention may be carried out by using two differentiated reactors, an oil phase reactor and a water phase reactor. The first reactor has a temperature regulating system and a stirrer, while the second mixing reactor or reactor in addition to the temperature control system has a disperser.

[0082] The emulsification may be carried out either with stirring, stirring and mechanical dispersion, stirring and rotor-stator (e.g., ULTRA TURRAX® type). The formulations of the present invention may be applied to a variety of insulation products for controlling the generation of dust during its manufacture. Besides, they can also be used to improve flexibility of polyflavonoid-based foams.

[0083] Thus, a further object of the invention is the use of a formulation according to the present invention in the manufacture of articles selected from fibreglass insulations, rock wool insulations, slag wool insulations or polyflavonoid-based foams.

[0084] More specifically, the invention refers to the use of the formulation herein described as anti-dust additive in the manufacture of insulations articles such as fibreglass insulations, rock wool insulations, slag wool insulations or a combination thereof.

[0085] The formulations may also be useful as internal mold release formulations. The formulations may for example be used in the manufacture of molded items, such as boards or panels, to avoid the adherence of fibres or chips, agglomerated with synthetic resins, to the metal parts of the process, thus reducing the degree of soiling of the manufacturing process.

[0086] The vegetable oil-based O / W emulsion formulation of the invention may also be useful as external mold release formulations. The formulations may for example be applied onto the surface of the layers or sandwich of fibres and / or chips and / or particles and / or fibreglass or rock wool, for example, but not limited to, by spraying, before being pressed in a press, during the manufacture of cellulose-derived boards, wood derived boards, fibreboards, particleboards, chipboards, oriented strand boards, fibreglass or rock wool, or combinations thereof.

[0087] Depending on its intended use, the formulation of the invention may be mixed with other additives commonly used for said uses. In particular, the vegetable oil-based formulation herein described may be mixed with adhesive resins commonly used in the manufacture of insulation products such as those based on fibreglass, wool rock or slag wool fibres such as, for example but not limited to, phenolic resins, acrylic resina, starch-based resins, sugar-based resins or a combination thereof. Formulations of the invention provide a great advantage in the manufacturing of articles selected from fibreglass, rock wool insulations or slag wool insulations because, in addition to its kinetical stability and anti-dust efficiency, are able to show a great compatibility those adhesive resins.

[0088] The invention also refers to articles treated or manufactured by using the vegetable oilbased formulation described in this document, as well as articles treated or manufactured by using the vegetable oil-based formulation obtained or obtainable by the method according to the invention. In particular embodiments, said articles are insulation products such as fibreglass, rock wool or slag wool insulation products, comprising the formulation as defined above and fibreglass, rock wool or slag wool fibres.

[0089] The term “about” when used in the context of the present invention preceding a number and referring to it, is to be understood as designating any value lying within the range defined by the number ±5%, more preferably a range defined by the number ±2%. For example, the expression “about 10” should be construed as “within the range of 9.5 to 10.5”, preferably “within the range of 9.8 to 10.2”. A skilled person in the art would unambiguously understand that the term “about” can also be understood as the value it is referring to, while applying the general convention in the scientific and technical literature, i.e., the last decimal place of a numerical value indicates its degree of accuracy, so that the maximum margin can be ascertained by applying the rounding-off convention to the last decimal place.

[0090] Through the description and the claims, the word “comprises” and variations thereof are not intended to exclude other technical features, ingredients or steps. Additional advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or may be learned by practice of the invention without undue burden.

[0091] BRIEF DESCRIPTION OF THE FIGURES

[0092] Figure 1a shows an image of an insulation fiberglass product manufactured with a formulation according to the invention, whereas figure 1b shows an image of another manufactured without said formulation.

[0093] Figure 2 shows a graph of the distribution of the Sauter diameter of the particles for the formulation E1 according to the invention, which were stored at normal conditions and tested at different points of time: months 1 , 2 and 6.

[0094] Figure 3 shows a graph of the distribution of the Sauter diameter of the particles for formulation E1 according to the invention and sample 2 of prior art reference W02009 / 046521 A1 (identified as Walker's emulsion E2), both samples were previously stored at normal conditions for 24 hours.

[0095] Figure 4 graphically represents the viscosity (triangles) and stress (squares) measured at different shear rates for the formulation according to the invention E1 , samples were previously stored at normal conditions for 24 hours. Figure 5 graphically represents the viscosity (triangles) and stress (squares) measured at different shear rates for the formulation according to the invention E6, samples were previously stored at normal conditions for 24 hours.

[0096] EXAMPLES

[0097] In the following, the invention will be further illustrated by means of Examples and Comparative Examples. The Examples should in no case be interpreted as limiting the scope of the invention, but only as an illustration of the invention.

[0098] Diverse formulations were prepared by direct O / W emulsion method.

[0099] Example 1 : preparation of a soybean O / W emulsion according to the invention (E1)

[0100] 472.00 g of water, 20.00 g of sodium naphthalene-2-sulfonate (Tamol® NN-3501 from BASF, a solution having a 38 wt. % solid content, the amount expressed is referred to sodium naphthalene-2-sulfonate on dry matter basis) and 8.00 g of ghatti gum (N°CAS: 9000-28-6) were mixed, introduced in a water phase reactor and heated at 75°C. 500.00 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 75°C. The oil phase was slowly added to the water phase at a rate of 20 g / min. The mixture was mixed at a stirring rate of 300 rpm for 20 min thus obtaining a pre-emulsion, which was then introduced in a singlephase homogenizer at a pressure of 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 4.5°C per minute, until reaching a temperature of 20-25°C. 1000 g of a liquid emulsion were obtained, having a viscosity of 300 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 53 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.62 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for at least 10 months, at normal pressure and temperature conditions.

[0101] Example 2: preparation of a rapeseed O / W emulsion according to the invention (E2)

[0102] 312.18 g water, 12.54 g of sodium naphthalene-2-sulfonate (Tamol® NN-3501 from BASF, a solution having a 38 wt. % solid content, the amount expressed is referred to sodium naphthalene-2-sulfonate on dry matter basis) and 5.28 g of ghatti gum (N°CAS: 9000-28-6) were mixed, introduced in a water phase reactor and heated at 80°C. 330.00 g of refined rapeseed oil (flash point 326°C, iodine value 125 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 80°C. The oil phase was slowly added to the water phase at a rate of 15 g / min. The mixture was mixed at a stirring rate of 250 rpm for 22 min. thus obtaining a pre-emulsion, which was then introduced in a singlephase homogenizer at 200 bar (20 MPa). Subsequently the mixture was cooled, at a rate of 6.0°C per minute, until reaching a temperature of 20-25°C. 660 g of a liquid emulsion were obtained, having a viscosity of 390 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 53 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.71 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for at least 10 months, at normal pressure and temperature conditions.

[0103] Example 3: preparation of a sunflower O / W emulsion according to the invention (E3)

[0104] 183.30 g water, 10.21 g of sodium naphthalene-2-sulfonate (Tamol® NN-3501 from BASF, a solution having a 38 wt. % solid content, the amount expressed is referred to sodium naphthalene-2-sulfonate on dry matter basis) and 4.30 g of ghatti gum (N°CAS: 9000-28-6) were mixed, introduced in a water phase reactor and heated at 75°C. 232.20 g of refined sunflower oil (flash point 319°C, iodine value 135 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 75°C. The oil phase was slowly added to the water phase at a rate of 10 g / min. The mixture was mixed at a stirring rate of 350 rpm for 30 minutes thus obtaining a pre-emulsion, which was then introduced in a homogenizer at a first phase of 150 bar (15 MPa) and a second phase of 30 bar (3 MPa). Subsequently the mixture was cooled, at a rate of 4.0 °C per minute, until reaching a temperature of 20-25°C. 430 g of a liquid emulsion were obtained, having a viscosity of 360 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 58 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.68 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for at least 10 months, at normal pressure and temperature conditions.

[0105] Example 4: preparation of a soybean O / W emulsion according to the invention (E4)

[0106] 577.50 g water, 25.00 g of a secondary alcohol ethoxylate (Tergitol 15 S-9® from DOW) and 10.00 g of ghatti gum (N°CAS: 9000-28-6) were mixed in a reactor and heated at 80°C. Then, 637.50 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were heated at 75 °C and then added to the water phase at a rate of 25 g / min. The mixture was mixed for 20 minutes at a stirring rate of 300 rpm and a temperature of 75 °C thus obtaining a pre-emulsion, which was then introduced in a single-phase homogenizer at 320 bar (32 MPa). Subsequently the mixture was cooled, at a rate of 7.0 °C per minute, until reaching a temperature of 20-25°C. 1250 g of a liquid emulsion were obtained, having a viscosity of 384 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 54 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.60 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for at least 10 months, at normal pressure and temperature conditions. to the invention

[0107] 687.83 g water, 6.75 g diethanolamine and 10.80 g of ghatti gum (N°CAS: 9000-28-6) were mixed in a water phase reactor and heated at 75°C. 634.50 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) and 10.13 g of C12-C22 alkyl fatty acid (from Radiacid 0075 from Oleon) were added to an oil phase reactor and heated at 75°C. The oil phase was slowly added to the water phase at a rate of 22 g / min. The mixture was mixed at a stirring rate of 300 rpm for 25 minutes thus obtaining a preemulsion, which was then introduced in a single-phase homogenizer at 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 5.0 °C per minute, until reaching a temperature of 20-25°C. 1350 g of a liquid emulsion were obtained, having a viscosity of 710 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 49 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.60 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for at least 10 months, at normal pressure and temperature conditions. to the invention

[0108] 463.68 g water, 13.80 g of sodium naphthalene-2-sulfonate (Tamol® NN-3501 from BASF, a solution having a 33.05 wt. % solid content, the amount expressed is referred to sodium naphthalene-2-sulfonate on dry matter basis) and 8.10 g of ghatti gum (N°CAS: 9000-28-6) were mixed, introduced in a water phase reactor and heated at 78°C. 207.00 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 78°C. The oil phase was slowly added to the water phase at a rate of 9 g / min. The mixture was mixed at a stirring rate of 300 rpm for 40 minutes thus obtaining a pre-emulsion, which was then introduced in a single-phase homogenizer at a homogenizer pressure of 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 5.0°C per minute, until reaching a temperature of 20-25°C. 692.58 g of a liquid emulsion were obtained, having a viscosity of 120 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 33 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.53 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for at least 10 months, at normal pressure and temperature conditions. to the invention 315.11 g water, 20.64 g of sodium naphthalene-2-sulfonate (Tamol® NN-3501 from BASF, a solution having a 38 wt. % solid content, the amount expressed is referred to sodium naphthalene-2-sulfonate on dry matter basis) and 8.26 g of ghatti gum (N°CAS: 9000-28-6) were mixed, introduced in a water phase reactor and heated at 80°C. 516.00 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 80°C. The oil phase was slowly added to the water phase at a rate of 20 g / min. The mixture was mixed at a stirring rate of 300 rpm for 28 minutes thus obtaining a pre-emulsion, which was then introduced in a singlephase homogenizer at a pressure of 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 4.0°C per minute, until reaching a temperature of 20-25°C. 860 g of a liquid emulsion were obtained, having a viscosity of 1500 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 63 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.62 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for at least 10 months, at normal pressure and temperature conditions.

[0109] Example 8: preparation of a soybean O / W emulsion accordinq to the invention (E8)

[0110] 424.00 g water, 15.20 g of sodium naphthalene-2-sulfonate (Tamol® NN-3501 from BASF, a solution having a 38 wt. % solid content, the amount expressed is referred to sodium naphthalene-2-sulfonate on dry matter basis) and 3.20 g of xanthan gum (N°CAS:11138-66-2) were mixed, introduced in a water phase reactor and heated at 75°C. 360.00 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 75°C. The oil phase was slowly added to the water phase at a rate of 15 g / min. The mixture was mixed at a stirring rate of 300 rpm for 35 minutes thus obtaining a pre-emulsion, which was then introduced in a single-phase homogenizer at a pressure of 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 5.0°C per minute, until reaching a temperature of 20- 25°C. 802,40 g of a liquid emulsion were obtained, having a viscosity of 780 cP (25°C, Viscosimeter Brookfield HV, spindle 02) and 47 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.64 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for at least 10 months, at normal pressure and temperature conditions. O / W emulsion maleic as surfactant bv direct O / W method

[0111] 399.36 g water, 15.6 g of styrene maleic anhydride copolymer (SMA) (XI RAN 3000H, from Polyscope) and 6.24 g of ghatti gum (N°CAS: 9000-28-6) were mixed, introduced in a water phase reactor and heated at 75°C. 358.80 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 80°C. The oil phase was slowly added to the water phase at a rate of 16 g / min. The mixture was mixed at a stirring rate of 300 rpm for 20 minutes thus obtaining a pre-emulsion, which was then introduced in a single-phase homogenizer at a pressure of 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 4.0°C per minute, until reaching a temperature of 20-25°C. 780 g of a liquid emulsion were obtained, having a viscosity of 180 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 49 wt.% of active matter. The particle size distribution was not gaussian with a Sauter diameter of 4.77 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for less than 1 week, at normal pressure and temperature conditions. O / W emulsion sulfate as surfactant bv direct O / W method

[0112] 560.05 g water, 23.00 g of sodium lauryl sulfate (from Brenntag) and 9.20 g of ghatti gum (N°CAS: 9000-28-6) were mixed, introduced in a water phase reactor and heated at 78°C. 557.75 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 78°C. The oil phase was slowly added to the water phase at a rate of 22 g / min. The mixture was mixed at a stirring rate of 300 rpm for 30 minutes thus obtaining a pre-emulsion, which was then introduced in a single-phase homogenizer at a pressure of 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 6.5°C per minute, until reaching a temperature of 20- 25°C. 1150 g of a liquid emulsion were obtained, having a viscosity of 930 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 51 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.46 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for less than 1 week, at normal pressure and temperature conditions.

[0113] Comparative Example 3: preparation of a soybean O / W emulsion using cellulose as rheological additive bv direct O / W method (CE3)

[0114] 659.92 g water, 29.20 g of sodium naphthalene-2-sulfonate (Tamol® NN-3501 from BASF, a solution having a 38 wt. % solid content, the amount expressed is referred to sodium naphthalene-2-sulfonate on dry matter basis) and 11.68 g of hydroxyethyl cellulose (N°CAS 9004-62-0) were mixed, introduced in a water phase reactor and heated at 80°C. 759.20 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 80°C. The oil phase was slowly added to the water phase at a rate of 25 g / min. The mixture was mixed at a stirring rate of 300 rpm for 30 minutes thus obtaining a pre-emulsion, which was then introduced in a single-phase homogenizer at a pressure of 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 4.0°C per minute, until reaching a temperature of 20-25°C. 1460 g of a creamy emulsion were obtained, having 55 wt.% of active matter. The emulsion was kinetically unstable since it became creamy in the homogenizer.

[0115] Comparative Example 4: preparation of a soybean O / W emulsion using an acrylic thickener as rheological additive by direct O / W method (CE4)

[0116] 433.80 g water, 11.40 g of sodium naphthalene-2-sulfonate (Tamol® NN-3501 from BASF, a solution having a 38 wt. % solid content, the amount expressed is referred to sodium naphthalene-2-sulfonate on dry matter basis) and 4.80 g of an acrylic thickener (Rheolate® 150 from Elementis Specialties) were mixed, introduced in a water phase reactor and heated at 70°C. 516 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 70°C. The oil phase was slowly added to the water phase at a rate of 25 g / min. The mixture was mixed at a stirring rate of 300 rpm for 25 minutes thus obtaining a pre-emulsion, which was then introduced in a single-phase homogenizer at a pressure of 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 6.0°C per minute, until reaching a temperature of 20-25°C. 966 g of a liquid emulsion were obtained, having a viscosity of 50 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 55 wt.% of active matter. The particle size distribution was not gaussian with a Sauter diameter of 6.34 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for less than 24 hours, at normal pressure and temperature conditions. O / W emulsion with low

[0117] 449.26 g water, 8.74 g of sodium naphthalene-2-sulfonate / (Tamol® NN-3501 from BASF, a solution having a 38 wt. % solid content, the amount expressed is referred to sodium naphthalene-2-sulfonate on dry matter basis) and 1.00 g of ghatti gum (N°CAS: 9000-28-6) were mixed, introduced in a water phase reactor and heated at 70°C. 200.00 g of refined soybean oil (flash point 317°C, iodine value 140 g of I2 per 100 g of oil) were introduced in an oil phase reactor and heated at 70°C. The oil phase was slowly added to the water phase at a rate of 23 g / min. The mixture was mixed at a stirring rate of 300 rpm thus for 22 minutes obtaining a pre-emulsion, which was then introduced in a singlephase homogenizer at a pressure of 300 bar (30 MPa). Subsequently the mixture was cooled, at a rate of 6.0°C per minute, until reaching a temperature of 20-25°C. 659 g of a liquid emulsion were obtained, having a viscosity of 18 cP (25°C, Viscosimeter Brookfield HV, spindle 02, 20 rpm) and 32 wt.% of active matter. The particle size distribution was gaussian with a Sauter diameter of 0.59 pm, measured by laser diffraction in a Mastersizer 300 equipment. The emulsion was kinetically stable for less than 24 hours, at normal pressure and temperature conditions.

[0118] Viscosity, particle size distribution and stability of the above-described examples are surmised in TABLE 1 (see below):

[0119] Compatibility with phenolic resins

[0120] In this study the compatibility of formulation of the invention with phenolic resins conventionally used in the manufacture of insulation products was tested. Procedure:

[0121] A basic phenolic resin (FORESA RES 3169) was adjusted to a temperature of 20 °C ± 1 °C and diluted until a 20 wt.% solid content. Then, 20 parts, on a dry basis, of the vegetable oil-based emulsion were added to the diluted resin solution and the mixture was stirred for 1 min with a magnetic stirring bar. Subsequently, the mixture was transferred to a test-tube of 100 ml and visually observed to determine if there was phase separation. If so, the separation percentage volume after 1 h, 24 h and 48 h was measured. There was also visually observed if the emulsion was broken down, i.e. , if small particles could be distinguished.

[0122] The compatibility with phenolic resins of formulations CE3-CE5 were not analysed because these formulations were not stable at its own.

[0123] Thus, it is proved that formulations according to the invention are compatible with phenolic resins conventionally used in the manufacture of insulation products.

[0124] Anti-dusting efficacy

[0125] In order to prove the anti-dusting efficacy of the formulation according to the invention, different molds of thermal insulation products were manufactured in the laboratory:

[0126] Mold (A) - using the vegetable-oil based formulation of the invention, and

[0127] Mold (B) - without anti-dusting agent.

[0128] Those molds were manufactured weighting 100 g of fiberglass, adding 6 g of a binder agent and, in the manufacture of mold (A), adding 2 g of the vegetable-oil based formulation of the invention. Mixing these ingredients and heating at 220°C for 5 minutes.

[0129] As can be visually observed in comparing figure 1a (mold A) and figure 1b (mold B), the thermal insulation product according to the invention is a more compacted piece, without dust in the surface thereof. The anti-dust effect can also be appreciated by touch, since mold A (according to the invention) does not release dust and, therefore, it does not scratch when touched, whereas mold A (without the formulation of the invention) does.

Claims

CLAIMS1. A vegetable oil-based formulation which is an oil in water (O / W) emulsion comprising:- about 30 wt.% to about 60 wt.% of at least one refined vegetable oil with a flash point higher than 260°C, measured according to ASTM D92-18;- about 1 wt.% to about 5 wt.% of at least one anionic surfactant, at least one nonionic surfactant or a combination thereof, wherein- the anionic surfactant is selected from aryl sulfonate, >Ci2 alkyl sulfate, >Ci2 alkyl carboxylate, alkaline salt of C10-C15 alkyl-aryl-sulfonic acid and a combination thereof, and- the non-ionic surfactant is selected from primary alcohol ethoxylate, secondary alcohol ethoxylate and a combination thereof, wherein said non-ionic surfactant has a HLB higher than 8;- about 0.2 wt.% to about 4 wt.% of at least one rheological additive which is an ionic polysaccharide, preferably selected from the group consisting of gum ghatti, xanthan gum and a combination thereof; and- water; wherein the formulation has an active matter content of about 31 wt% and about 69 wt% and the rest of the formulation, until reaching 100 wt.%, is water, the active matter content comprising all the components which are different from water; and wherein the viscosity of the formulation is of about 0.1 Pa s (100 cP) to about 1.5 Pa s (1500 cP), preferably about 0.15 Pa s (150 cP) to about 1.2 Pa s (1200 cP) (25°C, Viscosimeter Brookfield HV, 20 rpm).

2. The vegetable oil-based formulation according to claim 1 , wherein the refined vegetable oil is selected from the group consisting of refined soybean oil, refined sunflower oil, refined rapeseed oil, refined corn oil, refined palm oil and mixtures thereof.

3. The vegetable oil-based formulation according to claim 2, wherein the refined vegetable oil is refined soybean oil having a flash point, determined according to ASTM D92-18, higher than 260°C, preferably of about 300°C to about 350°C, and an iodine value, determined according to UNE-EN ISO 3961 :2018, of about 120 g to about 155 g iodine per 100 g of soybean oil.

4. The vegetable oil-based formulation according to any one of claims 1 to 3, wherein the surfactant is an aryl sulfonate surfactant, preferably a naphthalene sulfonate surfactant, and more preferably sodium naphthalene sulfonate.

5. The vegetable oil-based formulation according to any one of claims 1 to 4, wherein the S / O ratio, that is, the surfactant / total weight amount of oil ratio in the formulation, is of about 1 wt.% to about 10 wt.%.

6. The vegetable oil-based formulation according to any one of claims 1 to 5, wherein the active matter content is of about 45 wt.% to about 55 wt.%.

7. The vegetable oil-based formulation according to any one of claims 1 to 6, wherein the oil particles in the emulsion have a gaussian distribution with a Sauter mean diameter (D(3,2)) of about 0.5 pm to about 1.5 pm, measured by laser diffraction in a Mastersizer 300 equipment.

8. A method of manufacturing a vegetable oil-based formulation as defined in any one of claims 1 to 7, wherein the method comprises: a) obtaining a water phase comprising a rheological additive which is an ionic polysaccharide preferably selected from the group consisting of gum ghatti, xanthan gum and a combination thereof and, optionally, at least one anionic or non-ionic surfactant as defined in any one of claims 1 , 4 or 5; b) obtaining an oil phase comprising at least one refined vegetable oil with a flash point higher than 260°C and, optionally, at least one anionic or non-ionic surfactant as defined in any one of claims 1 , 4 or 5; wherein at least one of the water phase or the oil phase comprises at least one surfactant as defined in any one of claims 1 , 4 or 5; c) heating the water phase and the oil phase at a temperature equal to or higher than about 70°C, preferably of about 70 to about 80°C; d) adding the heated oil phase to the heated water phase and stirring the mixture at a temperature equal to or higher than about 70°C, preferably of about 70°C to about 80°C, for at least 20 minutes;e) homogenizing the mixture of step d); and f) gradually cooling the homogenized mixture of step e) until a temperature of 20°C to 30°C; wherein the surfactant, rheological additive, refined vegetable oil and water are added in such an amount to obtain a formulation as defined any one of claims 1 to 7.

9. The method according to claim 8, wherein- the formulation comprises at least one anionic surfactant selected from aryl sulfonate, >Ci2 alkyl sulfate, >Ci2 alkyl carboxylate, alkaline salt of C10-C15 alkyl-aryl-sulfonic acid and a combination thereof, preferably a naphthalene sulfonate surfactant, more preferably sodium naphthalene sulfonate; and said anionic surfactant is comprised in the aqueous phase obtained in step a); and / or- the formulation comprises at least one non-ionic surfactant selected from primary alcohol ethoxylate, secondary alcohol ethoxylate and a combination thereof, wherein said non-ionic surfactant have a HLB higher than 8; and said non-ionic surfactant is comprised in the oil phase obtained in step b).

10. The method according to any one of claims 8 or 9, wherein- the oil phase is added to the water phase in a period of about 10 minutes to about 40 minutes;- the mixture obtained by addition of the heated oil phase to the heated water phase in step d) is stirred at a rate of 30 rpm to 350 rpm for at least 20 minutes;- the homogenization of step e) is carried out in a homogenizer at a pressure of about 30 bar (3 MPa) to about 350 bar (35 MPa) preferably for a period of 1 min to 30 min; and / or- the homogenized mixture is gradually cold at a rate of 1 to 7 °C / min in step f), preferably of 4 to 7 °C / min.11 . Use of a formulation as defined in any one of claims 1 to 7, or a formulation obtained by the method as defined in any one of claims 8 to 10, in the manufacture of articles selected from fibreglass insulations, rock wool insulations, slag wool insulation products or polyflavonoid-based foams.12 Use according to claim 11 , wherein the formulation is used as anti-dust additive in the manufacture of fibreglass, rock wool or slag wool insultations.

13. Use according to claim 11 , wherein the formulation is used to increase flexibility of a polyflavonoid-based foam.

14. Article manufactured by using a formulation as defined in any one of claims 1 to 7, or a formulation obtained by the method as defined in any one of claims 8 to 10, wherein said article is selected from fibreglass insulations, rock wool insulations and slag wool insultations.

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