BR112019009252B1 - VEGETABLE OIL-BASED O/W FORMULATIONS OBTAINABLE FROM RENEWABLE SOURCES TO INCREASE HYDROPHOBICITY OF WOOD-DERIVED BOARDS AND STONE WOOL OR FIBERGLASS INSULATIONS - Google Patents

Abstract

These are vegetable oil-based formulations that comprise an O/W suspension, which are useful for increasing the hydrophobicity of wood-based boards and stone wool or fiberglass insulation, that is, for preparing water-repellent formulations; The formulations are kinetically stable and can be used in the manufacture of wood-based boards, fiberboards, particleboards, compacted boards, oriented particle boards, cardboards, fiberglass or stone wool. Uses of vegetable oil-based formulations. Plates and insulation obtained by using the formulations.

Description

FIELD OF INVENTION

[0001] The present invention relates to O/W formulations based on vegetable oil, an environmentally friendly alternative to formulations based on waxes derived from mineral oil or synthetic waxes, such as, for example, paraffin, which are obtainable from renewable resources instead of non-renewable resources; they comprise an O/W suspension or emulsion, which contains hydrogenated or partially hydrogenated palm oil and soybean oil, as well as surfactants and water, and are useful for increasing the hydrophobicity of wood-based boards and stone wool insulation or fiberglass. The formulations are useful for preparing water-repellent formulations, i.e., waterproofing formulations, and for enhancing the release of mold plates used during manufacturing, i.e., for preparing release formulations; the formulations are kinetically stable and can be used, for example, but without limitation, in the manufacture of wood-based boards, fiberboards (including MDF and HDF boards, i.e. medium density and high density fiberboards) , particleboards, compacted boards, oriented particle boards, plywood, cardboards and boards or insulation produced from fiberglass or stone wool. The invention also relates to materials treated or manufactured with the formulations of the invention, for example, panels and plates obtained through the use of said formulations. Since the aforementioned boards and insulations are generally manufactured with the use of formaldehyde-derived resins to bind the natural and/or synthetic fibers therein, the invention also relates to vegetable oil-based O/W formulations comprising formaldehyde scavengers. and/or catalysts for the hardening of resins derived from formaldehyde, so that, simultaneously with the waterproofing of the panels or manufactured insulation, the emission of formaldehyde from the plates is reduced and/or the hardening of the resins derived from formaldehyde is accelerated, conveniently without the need to add any additional formaldehyde scavengers and/or any additional catalysts for hardening formaldehyde-derived resins during the manufacture of the boards or insulation.

BACKGROUND OF THE INVENTION Use of paraffin wax

[0002] A compacted board panel is understood as any type of panel produced from small pieces of wood, such as chips, particles or fibers in which a binder is used in the manufacture thereof. The addition of paraffin wax plays a major role in this process as, in the form of a suspension, it largely enhances the effectiveness of this coating due to its inherent hydrophobic nature, thus helping the panel to avoid water absorption, minimizing the loss of physical and mechanical properties and improving the dimensional stability of the wood, reducing the swelling of the boards.

[0003] Wax-based suspensions derived from petroleum are used in many industrial applications, for example, to coat cellulose fibers, products such as paper and wood, mainly to provide moisture resistance, etc.

[0004] The use of waxes goes back to ancient times. For centuries, those most frequently used have been animal-based, insect-based, or vegetable-based waxes (whale oil, beeswax, carnauba wax); Currently, its use is significantly low and is intended for use as fuel (candles), artistic (paints and molding), cosmetic or medicinal (waxing and creams). Currently, emulsified waxes have been replaced by those of mineral origin (petroleum).

[0005] There are many applications of paraffin wax due to its versatility, and it is possible to provide as examples such varied fields and applications as the manufacture of candles, cheese coatings, matchsticks, paper and cardboard, hot melt adhesives, petroleum jelly, paraffin suspensions (often also called paraffin emulsions) for plaques, rubber protection, floor waxes, filler compound for telecommunications cables, reproductions of costumes and models, pathological and dental anatomical molds, polishes, protection bodywork, textile industry, chewing gum, explosives and powders, agricultural grafts, releasing agents, etc.

[0006] To date, the use of liquid paraffin or petrochemical agent-based paraffin suspensions is described in all manufacturing processes for compacted board panels, both with particles and fibers. The emulsification techniques applied so far in the wood-based panel manufacturing sector describe the use of petroleum-derived waxes and synthetic waxes for their incorporation into suspensions, however, they do not mention the use of vegetable-derived waxes in suspensions.

[0007] Although often referred to as paraffin emulsions, even commercially, in reality, these are paraffin suspensions, since the oily particles in the aqueous phase of O/W suspensions, under normal temperature and pressure conditions, are in the solid state . (For additional information, see, e.g., Paul Becher. “EMULSIONS, theory and practice.” Editorial Blume. 1972; Kozo Shinoda and Stig Friberg, “Emulsions and Solubilization.” John Wiley&Sons. 1986; Alton E. Bailey. “Industrial oil and fat products”. Editorial REVERTÉ, SA. 1984; Ankur Gupta et al., “Nanoemulsions: formation, properties and applications”. Soft Matter, 2016, 12, 2826 - 2841; Paqui Izquierdo et al., “Phase Behavior and Nano-emulsion formation by the Phase Inversion Temperature Method”, Langmuir 2004, 20, 6594-6598; R. Mujica Garai et al., “Study on the Effect of Raw Material composition on Water-Repellent capacity of Paraffin Wax Emulsions on Wood” , Journal of dispersion Science and Technology, 26:9-18, 2005; Mújila-Garai, R. et al., “Stabilization of Paraffin Emulsions Used in the Manufacture of Chipboard Panels by Liquid Crystalline Phases”. Journal of Dispersion Science and Technology , 28:6, 829-836, 2007;P. Izquierdo et al., “Formation and Stability of Nano-Emulsions Prepared Using the Phase Inversion Temperature Method”, Langmuir 2002,18,26-30; Weirong Liu et al., “Formation and stability of paraffin oil-in-water nanoemulsions prepared by the emulsion inversion point method.” Journal of Colloid and Interface Science 303 (2006) 557-563)

Vegetable-based O/W suspensions

[0008] The objective of the present invention is to obtain formulations comprising O/W suspensions with the use of a vegetable-based product as the main raw material, that is, suspensions based on the suspension of vegetable oils, such as palm oil and soybeans, in an aqueous phase.

[0009] These raw materials help reduce dependence on mineral oil (petroleum), reduce the carbon footprint and avoid price fluctuations of raw materials indexed to oil prices. Mineral oil is a non-renewable resource while vegetable oil is a renewable resource; therefore, vegetable oil-based formulations are environmentally friendly.

[0010] To date, no vegetable-based emulsion has been developed, which is viable from the point of view of producing compacted board and MDF panels, which can compete both in terms of cost and accessibility of materials. raw materials, as well as the final product results, with traditional paraffin-based products.

[0011] Currently, the increase in the production of palm and soybean crops due to the use of vegetable oils as substitutes for mineral oils has caused a decrease in the cost of raw materials, which makes them even more interesting to develop emulsions based on such vegetable oils.

[0012] The different vegetable wax emulsions have been described in the bibliography.

[0013] For example, US 7,267,743B2 (US 2006/0289138A1) and US 7,776,928B2 (US 2007/0068642A1) relate to wax emulsion coating applications, which comprise a vegetable wax that necessarily has a high hydrogenation level, that is, a high saturation, namely with an iodine value less than 10 and between 2 and 5, respectively. Although a variety of hydrogenated waxes are described therein, including castor, soybean, palm, corn, cottonseed, rapeseed, canola, sunflower, palm kernel, coconut, crambe, linseed and peanut, only soybeans and a mixture of soybeans and castor are exemplified. The resulting emulsions, when viewed on a glass slide, are said to appear uniform with only minute amounts of wax particles observed; although emulsions are said to be stable, the presence of wax particles, even in minute quantities, is a clear sign of the emulsions' lack of kinetic stability; in fact, in Example 8 of US 7,776,928B2, stability is defined as the property of the emulsion not to separate into its component phases over a specific period of time, however, the presence of wax particles reveals the opposite, even if it is present in minimal quantities. Wax emulsions are mainly used for coating paper or cardboard.

[0014] Other emulsions described include the use of toxic or currently banned surfactants, such as ethoxylated nonylphenols (US 7776928 B2). There are also emulsions with low concentrations that are commercially unavailable or have much higher costs than traditional paraffins, which makes them invalid for the industrial production of compacted board panels.

[0015] Document WO2010/054467 refers to stable emulsions for use as a formaldehyde scavenger, the emulsions comprising a wax and a formaldehyde scavenger. Although it is said that the wax can be a vegetable-derived wax or a natural oil, the inventors have not prepared any emulsions based on vegetable-derived waxes or natural oils, but only emulsions based on paraffin, which is the state standard. of the technique. The possibility of preparing such stable vegetable oil-derived emulsions has not been shown, and even less how to prepare such stable vegetable oil-derived emulsions nor their performance in the manufacture of plates or insulation.

Paraffin

[0016] Paraffins are saturated hydrocarbons that originate from the vacuum distillation of mineral oil and the subsequent refining stages to which the fractions or cuts are subjected to obtain lubricating oils. A vacuum distillate of crude paraffin has a composition with a significant proportion, approximately 15% by weight, of paraffins, which are solid at room temperature and therefore must be separated so that lubricating oils have freezing points equal to or below -10°C.

[0017] Linear carbon chains with lengths between C20 and C60, accompanied by chains that have branches from C1-C6 and saturated cycles with 5 or 6 carbon atoms, are mainly predominant in paraffin waxes.

[0018] Depending on the structural format of the chain, there are two types of paraffins: - Normal or linear chain paraffins (n-paraffins). They are saturated alkanes with a practically linear molecular structure. Its chemical formula is Cn H2n+2, where n>20 and its molecular weights are between 280 and 840. - Isoparaffins or branched-chain paraffins. These are saturated hydrocarbons (alkanes), whose structure mainly contains branched chains. These branches are mainly made up of linear radicals, C1-C6 or cycles with 5 or 6 carbons.

[0019] Paraffin classification is very varied as it is carried out depending on different properties: - Origin. - Crystalline nature (degree of crystallinity, depending on the hydrocarbons present). - Oil content (depending on the production process or degree of deoilification). - Degree of refining (depending on the final purification process, for the same oil content).

[0020] Paraffins, as described, form long molecular chains. These chains are more or less flexible and mobile; The grid they establish is characterized by the statistical variation of its dimensions and orientation, making it impossible to have the typical crystalline structure, which consists of the repetition of a unit called a cell. In any case, it is common to find regions in which the chains are in more or less parallel arrangements and packed into crystals, accompanied by amorphous regions.

Paraffin suspensions

[0021] As indicated above, paraffins are solid at room temperature; Their use as sealing or releasing agents involves a prior melting process with the resulting energy costs. The objective sought with paraffin wax suspensions is to obtain liquid paraffins at room temperature. Considering that paraffins are immiscible with water, the only way to combine both elements is through the formulation of water-based suspensions.

[0022] Suspensions are produced through the addition of emulsifying additives that form micelles to keep the suspensions thus stabilized both stable and liquid. These pre-emulsions are passed through a homogenizer at 200-300 atm (colloid mills or homogenizers) to achieve microscopic particle sizes, generally smaller than a micron, which maintain emulsion stability with a very narrow particle size distribution. .

[0023] These paraffin suspensions are easy to transport in liquid state at room temperature and enable perfect dosing in industrial installations; its primary use is as a waterproofing agent in the manufacture of compacted board and MDF (medium density fiberboard) panels. If these panels do not incorporate a waterproofing additive, major absorption and swelling problems arise as a result of ambient humidity due to the fibers or scrapings of the wood that make up the panel. The aminoplastic resins commonly used in panel manufacturing do not provide sufficient waterproofing on their own.

[0024] In the past, large panel manufacturing industries began to use molten paraffins as waterproofing systems. Considering the high energy and storage cost that this requires, paraffin suspensions seem to be a suitable alternative, hence their significant increase over recent years. Paraffin wax dosed in panel manufacturing in the form of a suspension or emulsion forms an anti-humidity barrier, both on the surface and inside. In this way, these panels can even be used as external plating, without causing swelling phenomena that would deform the panel.

[0025] Suspensions used in this field must have the following properties: • Good compatibility with aminoplastic resins. • Good water barrier behavior, waterproofing agent. • Good mechanical stability.

Palm Stearin and Hydrogenated Palm Oil

[0026] Stearin is obtained through the separation of Olein in the raw material, which is palm oil, while hydrogenated fats are obtained through different degrees of hydrogenation of the raw material, which is palm oil, transforming the double bonds (unsaturated) into single bonds (saturated).

[0027] The preparation of suspensions, dispersions or emulsions based on palm stearin and hydrogenated palm oil has technological difficulties or risks such as: 1. Poor stability of dispersions, leading to phase separation. 2. High viscosities that prevent their industrial application. 3. The concentration of waxes in stable suspensions is very low, around 30%. 4. Strong tendency to form a cream, which develops in a matter of hours. 5. The waterproofing capacity in some cases is lower than that of state-of-the-art paraffin emulsions.

[0028] Waxes are generally considered to be mixtures of esters with high molecular masses formed by acids fatty acids and monohydroxylated alcohol, which neither represent the number of times the CH2 group is repeated. Therefore, the most frequent values are: n = 8-18 and m = 16-36. (general structure of a wax)

[0029] Glycerides are made up of fatty acids with a high molecular mass and trihydroxylated alcohols such as propanetriol, glycerol or glycerin.

[0030] Glycerides can have an esterified hydroxyl group, called monoglyceride, diglyceride when they have two esterified hydroxyl groups and triglyceride when three hydroxyl groups have been esterified.

[0031] When glycerides have saturated carbon chains, they are called fats, all carbon atoms exhibit sp3 hybridization, except for the carbon of the functional group (ester), from which it can be deduced that the fatty acids in these structures are saturated chains.

[0032] In general, vegetable oils are characterized by the presence of double bonds in the fatty acid chains that form the glyceride structure and, therefore, not all carbon atoms exhibit sp3 hybridization, a new functionality arises, in which the carbon atoms exhibit sp2 hybridization and different chemical reactivity and the fatty acids present are not saturated. It is observed that saturated fatty acids have a specific packaging or order in the triglyceride molecules, which explains why fats are solid substances, while the particular stereochemistry of the fatty acids that constitute oils (unsaturated fatty acids) with geometric isomers, the The most abundant being the cis isomer, it provides a different spatial order, which can be seen in the Figures below. (It may be in solid state under normal conditions) (May not be in solid state under normal conditions)

[0033] Simple lipids are neutral substances, which are soluble in organic solvents with a low polarity, insoluble in water, with characteristic odors and their consistency varies from oily liquids, to semisolids, to solid substances.

[0034] Its insolubility in water is the property that is interesting for use as a waterproofing agent in the manufacture of compacted board and MDF panels. The challenge is to develop an ideal formula of a water-based nanosized oil suspension with a high concentration.

[0035] The properties of lipids, such as acidity, degree of saturation and ease of saponification, are related to their chemical structure. These properties can be determined using the following values: • Iodine value: grams of iodine that are added to 100 g of fat or oil. It measures the saturation level of fat or oil. • Acid value: the value of potassium hydroxide in milligrams needed to neutralize 1 g of fat or oil. It is a measurement of the acidity of simple lipids. • Saponification value: milligrams of potassium hydroxide needed to saponify 1 g of fat or oil. The acids present in the structure of simple lipids are monocarboxylic acids, having a carboxyl group and chains that vary in length from 4 to 40 carbon atoms, the most abundant being acids with 16 to 18 carbon atoms.

Manufacturing of wood composite boards

[0036] The manufacture of wood composite boards such as particleboards, fiberboards (MDF and HDF), compacted boards, oriented particle boards and the like generally comprises, first, combining wood chips, fibers or particles, optionally in combination with fibers synthetic materials and an adhesive. The mixture is then heated under pressure to cure the adhesive and to form the desired plate. Formaldehyde-based resins such as phenol-formaldehyde (PF) resins, urea-formaldehyde (UF) resins, and melamine-urea-formaldehyde (MUF) resins are typical adhesives or binders used in the manufacture of these panels.

[0037] To provide hydrophobization characteristics to wood composite boards, it is known in the prior art to include a wax emulsion in the board manufacturing process. Thus, once the plaque is produced, the wax provides hydrophobic properties to it and serves to repel water so that it is not absorbed, thus preventing the deterioration of the plaque.

[0038] Wood composite boards, as well as stone wool or fiberglass insulation, manufactured with formaldehyde-based adhesives, are known to result in formaldehyde emissions, both during manufacturing and, even later, throughout of time. It is a generally known fact that formaldehyde is a strong irritant and an allergenic agent and is also classified as a carcinogen.

Manufacture of fiberglass insulation and stone wool insulation

[0039] The manufacture of stone wool and fiberglass insulation products generally comprises a step of manufacturing the stone wool and fiberglass themselves, which can be carried out by different procedures, for example, according to known techniques in the state of the art as a rotating process (internal centrifuge), cascade process (external centrifuge) and flame attenuation process (container and marble).

[0040] To ensure the assembly and adhesion of the fibers, an adhesive resin, generally a thermosetting resin, is projected onto the fibers (glass fiber or stone wool) or mixed with the fibers. The mixture of fibers and resin is subjected to heat treatment, at a temperature generally above 100 °C, to effect polycondensation of the resin and, thus, obtain a thermal and/or acoustic insulation product. Commonly used adhesive compositions are formaldehyde-derived resins, similar to those used in the manufacture of wood-based boards or wood composite boards. During manufacturing, additional additives may be added to the fiber and adhesive mixture such as catalysts to cross-link the resin or waterproofing emulsions (typically paraffin-based).

[0041] In other words, the manufacture of fiberglass insulation and stone wool insulation has many similarities with the manufacture of wood-derived boards or wood composite boards.

Formaldehyde

[0042] Formaldehyde is a monomer, which is used to polymerize with urea, melamine, phenol to form aminoplastic resins. Formaldehyde has been under discussion as an indoor air pollutant since the 1960s (O. Wittmann 11962), Holz Roh-Werkst., 20, 221 - 224), when the release of formaldehyde from pellets during use was documented. The adverse health effects of indoor exposure to formaldehyde, especially irritation of the eyes and upper airways, were first reported in the mid-1960s. Formaldehyde emissions from materials bonded to urea formaldehyde resin were soon identified. as the cause of the complaints. As a consequence, a guideline value of 0.1 ppm was already proposed in 1977 by the former German Federal Health Agency to limit human exposure in housing. Criteria for limiting and regulating formaldehyde emissions from wood-based materials were established in 1981 in Germany and Denmark. Other countries followed and issued regulations in the mid-1980s. Formaldehyde was identified as one of the priority indoor air pollutants (Spengler J.D. et al. (1983). Science, 221(4605), 9-17). In parallel, the first studies on the carcinogenicity of formaldehyde triggered an avalanche of scientific work.

[0043] REACH (Registration, Evaluation, Authorization and Restriction of Chemical Agents) came into force in 2007. This is the main framework for chemical regulation in the European Union and is adopted to improve the protection of human health and the environment against risks that can be generated by chemical agents. REACH not only applies to those chemical agents used in industrial processes, but also to chemical agents in products intended for use at a customer site, for example, building materials, textile products, consumer goods and other appliances.

[0044] The European Chemical Agents Agency requests the provision of a Chemical Safety Report (CSR) for products manufactured using formaldehyde, following the “DECISION ON SUBSTANCE EVALUATION PURSUANT TO ARTICLE 46(1) OF REGULATION (EC) NO 1907/2006 for formaldehyde, CAS No 50-00-0 (EC No 200-001-8)”.

[0045] The International Agency for Research on Cancer (IARC) classified formaldehyde as a human carcinogen (Group 1) in 2004. The definition of a Group 1 carcinogen according to IARC is as follows: “There is sufficient evidence to conclude that it can cause cancer in humans”. The assessment is based on information regarding the relationship between nasopharyngeal cancer and leukemia related to formaldehyde exposure (International Agency for Research on Cancer (IARC), 2006). The European Commission classified formaldehyde as a type 1B carcinogen and 2 mutagen on June 5, 2014 in EU ordinance 605/2014. Category 1B states that the carcinogenic effect has been demonstrated in animal tests and is probable in humans. Reclassification results in a series of consequences depending on national legislation.

[0046] For the work area the Scientific Committee on Occupational Exposure Limits (SCOEL) recommended an 8-hour TWA (time weighted average) of 0.3 ppm and a STEL (Short Term Exposure Limit) of 0. 6 ppm (Scientific Committee on Occupational Exposure Limits (SCOEL), 2015). SCOEL considers formaldehyde to be a Group C carcinogen (genotoxic carcinogen with a threshold based on mode of action). The German MAK Commission (Deutsche Forschungsgemeinschaft (DFG), 2016) also sets a maximum workplace concentration of 0.3 ppm and classifies formaldehyde as a Group 4 carcinogen (substances that cause cancer in humans or animals or that are considered to be carcinogenic to humans and for which a MAK value can be derived). The German Federal Institute for Occupational Health and Safety (BAuA) argues that current literature indicates formaldehyde exposure concentrations without adverse effects, which supports the assumption of a threshold concentration and allows the derivation of an occupational threshold value ( Bundesanstalt für Arbeitsschutz und Arbeitsmedizin (BAuA), 2015).

[0047] WHO confirmed its internal guideline value for formaldehyde as 0.1 mg/m3 in the year 2010 (World Health Organization, 2010). The WHO assessment was studied thoroughly in an additional study and an air quality formaldehyde guideline of 0.1 mg/m3 was found to be protective against both acute and chronic sensory irritation to the airways in the general population (Nielsen GD et al. (2010), Arch Toxicol., 84, 423-446). Furthermore, the same authors state that the WHO guideline value of formaldehyde is also considered tenable for the prevention of all types of cancer, including lymphohematopoiesis malignancies.

[0048] In 2016, Germany adopted the WHO guideline value. The Committee on Internal Guideline Values outlined the following: “Based on a NOAEC (no observed adverse effect concentration) of 0.63 mg/m3 for sensory irritation in humans, a factor of 1 for time extrapolation and a factor of 5 for inter-human variability, the Committee derives a precautionary indoor air guide value (RW I) of 0.1 mg formaldehyde per cubic meter...In conclusion, the indoor air guide value for formaldehyde it is also protective against the risk of cancer from inhaled formaldehyde” (Ausschuss für Innenraumrichtwerte, 2016a). The same committee stated that, based on current data, there is no clear association between indoor formaldehyde exposure and asthma in children (Ausschuss für Innenraumrichtwerte, 2016b).

[0049] Over the years, numerous national authorities have also reevaluated their indoor air guide line values (Salthammer et al. (2011), Chemosphere, 82(11), 1507-17) and subsequently intend to agree with the recommendation of WHO of 0.1 mg/m3. This harmonization is a pragmatic step since the value of WHO is very well evaluated and justified. Furthermore, the guideline value is also not normally restrictive as formaldehyde conditions in normal vital conditions tend to average between 0.02 and 0.04 mg/m3 (Salthammer T et al. (2010), Chem Rev. 110, 2536-2572). According to the currently available state of the art, a guideline to the WHO guideline value of 0.1 mg/m would appear sensible, practicable and toxicologically defensible (Salthammer et al (2015), Int J Hyg Environ Health. 218(4),433-6). The argument is supported by Nielsen et al. (2013), Arch Toxicol., 87, 7398. These authors evaluated current guideline approaches and came to the conclusion that the WHO guideline has been strengthened.

[0050] Therefore, an ongoing objective is to absorb or "sequestrate" the formaldehyde contained in wood composite boards and/or generated during the manufacture of such boards, or during the manufacture of other materials, such as boards or other insulation articles produced from from stone wool or fiberglass.

Formaldehyde emissions: test method

[0051] Many organizations have defined the test method with which the level of formaldehyde emissions should be determined:

[0052] UNE-EN ISO 12460-3:2016: the gas analysis method, which is an updated version from wood-based panels - Determination of formaldehyde release – Part 3: Gas analysis method (ISO 12460-3:2015).

[0053] TSCA Title VI provides quarterly testing and quality control for solid wood plywood, particleboard and MDF using specified methods developed by ASTM International, among which, it is worth noting:

[0054] ASTM D5582-00 (Reapproved 2006), Standard Test Method for Determining Formaldehyde Levels of Wood Products Using a Desiccator. This test method describes a small-scale procedure for measuring the potential for formaldehyde emissions from wood products. The formaldehyde level is determined by collecting atmospheric formaldehyde in a small distilled water reservoir within a closed desiccator. The amount of formaldehyde is determined by a chromotropic acid test procedure.

[0055] ASTM D6007-02, the Standard Test Method for Determining Airborne Formaldehyde Concentrations of Wood Products Using a Small-Scale Chamber. This test method measures airborne formaldehyde concentrations from wood products under defined test conditions of temperature and relative unit. The results obtained from this small-scale chamber test method are intended to be comparable with the results obtained by testing larger product samples using the large chamber test method for wood products, Test Method E 1333.

[0056] ASTM E1333-10, Standard Test Method for Determining Air Formaldehyde Concentrations and Emission Rates from Wood Products Using a Large Chamber. This test method measures the concentration of formaldehyde in the air and the emission rate of wood products containing formaldehyde under conditions designed to resemble the use of the product. Air concentration and emission rate are determined in a large chamber under specific test conditions of temperature and relative unit. The general procedures are also intended for testing product combinations at product loading ratios and at air exchange rates typical of the indoor environment.

[0057] BS EN 120:1992, Wood-based panels. Determination of formaldehyde content - Extraction method called punch method, English version. This European standard describes an extraction method, known as the punch method, for determining the formaldehyde content of unlaminated and uncoated wood-based panels.

[0058] UME-EN ISO 12460-3:2016, Wood-based panels — Determination of formaldehyde release — Part 2: Formaldehyde release by gas analysis method, English version. This European standard describes a procedure for determining accelerated formaldehyde release from wood-based panels.

[0059] JIS A 1460:2001 Building boards - Determination of formaldehyde emission - Desiccator method: This method describes a method for testing formaldehyde emissions from building boards by measuring the concentration of formaldehyde absorbed in distilled water or deionized from samples of a specified surface area placed in a glass desiccator for 24 hours.

Formaldehyde scavengers

[0060] Various compounds useful as formaldehyde scavengers are known in the prior art, such as, for example, urea, urea derivatives, urea resins, sodium metabisulfite, ammonium bisulfite.

[0061] Document WO 2010/054467 A1 describes emulsions that have a high wax content, comprising formaldehyde scavengers; formaldehyde scavengers are preferably selected from urea, a urea derivative, urea resin, urea-formaldehyde resin, a melamine-urea-formaldehyde resin, an ethyleneurea compound, carbohydrazide, a natural polyphenol , tannin, lignin, lignosulfonate or a combination thereof.

[0062] Other work studies (Costa et al. (2013), Wood Sci Technol (2013) 47: 1261-127) present the performance of sodium and ammonium bisulfite as formaldehyde sequestrants in the production of particleboard and MDF; however, the use of these types of sequestrants causes an excessive loss of mechanical properties in the final product that does not sustain the current market.

[0063] Another known way to reduce formaldehyde emission from plaques is to reduce the molar ratio of formaldehyde/urea; in fact, this was a strategy adopted in recent decades to reduce formaldehyde emissions (Myers GE et al. (1984), For Prod J 34 (5):35- 41). However, this reduction reduces the reactivity of urea-formaldehyde (UF) resins. Currently, the reactivity of industrial UF adhesives is close to the minimum limit accepted for industrial panel production (urea, a urea derivative, a urea resin, a urea-formaldehyde resin, a melamine-urea-formaldehyde resin, a compound of ethyleneurea, carbohydrazide, a natural polyphenol, tannin, lignin, lignosulfonate or a combination thereof.).

[0064] The replacement of UF resins with other formaldehyde-free adhesives does not convince industrial producers, due to their higher price or lower reactivity (Amazio P et al. (2011), J Appl Polym Sci 122(4):2779 -2788); Despres A et al. 22010), Eur J Wood Prod 68(1):13-20; Tang L et al. 20 011), Int J Adhes Adhes 31 (6):507-512). To increase the degree of curing and reduce free formaldehyde at the end of curing, new catalysts were studied, however, the reactivity is still very low (Costa et al. (2012), Int Wood Prod J. 4(4), 242- 247; Gunnells D et al. (1998), Catalyst systems. In: Bradfield J (ed) Resin and blending seminar procedures, Portland, Oregon and Charlotte, North Carolina. For Prod Soc, page 176).

[0065] The use of sequestrants, for example, natural or biobased sequestrants (Eom Y-G et al. (2006), Mokchae Konghak 34:29-41; Kim S et al. 21(002); Constr Build Mater 23(6) , 2319-2323; Kim S et al. 02006), Macromol Mater Eng 291(9), 1027-1034) or other compounds that have a good affinity to capture formaldehyde (Boran S, et al. (2011), Int J Adhes 31 (7), 674-678; Costa et al. (2012), Journal International Wood Products Journal, Volume 4, Issue 4, Pages 242-247; Park et al. (2008), J Appl Polym Sci 110(3) : 1573 - 1580), to reduce formaldehyde emission from wood-based boards, is commonly adopted.

[0066] “Sodium metabisulfite as an air pollutant sequestrant for wood-based construction materials”, N A Costa et al., International Wood Products Journal, Volume 4 (2013), Issue 4, pages 242-247, study The different applications of sodium metabisulfite as a formaldehyde sequestrant, however, do not provide an in-depth analysis of the loss of mechanical properties and water resistance of the board, which means that this option is not viable at an industrial level. Furthermore, from the point of view of REACH, ammonium bisulfate is a dangerous substance; Handling this substance involves significant measures to prevent workers from breathing sulfur oxides in the air.

[0067] “Formaldehyde emission in wood-based panels: the effect of curing reactions”, N. A. Costa et al., International Wood Products Journal, Volume 5 (2014), Issue 3, pages 146-150 studies the effect of hexamine as a formaldehyde catalyst scavenger, the use of acid catalysts versus latent catalysts, and their pros and cons. It establishes that the combination of citric and oxalic acids in solid form with latent ammonium sulfate catalysts is the best solution, combined with a low molar ratio resin, to obtain values lower than 4 mg of formaldehyde per 100 g of board. dry, applying the EN120 punch method.

[0068] The molar ratio of the resins used is very low: 0.90 moles of formaldehyde per mole of urea. In the article, the tensile mechanical properties are too low for the industrial quality standards accepted by the EPF (European Panel Federation).

[0069] In the conclusions of the article itself, the need to find new formaldehyde catalyst sequestrant systems that meet the requirements in terms of mechanical properties and formaldehyde emission from the plate is justified, which confirms that achieving a solution that satisfies these requirements is currently an industrial challenge.

[0070] “Scavengers to achieve zero formaldehyde emission from wood-based panels”, Nuno A. Costa et al., Wood Science and Technology (2013), 47, pages 1261-1272, examined the performance of three scavengers of formaldehyde known in the manufacture of plates: sodium metabisulfite, ammonium bisulfite and urea. To obtain low formaldehyde emission values by the desiccator method (JIS method), more than 5% of the catalyst must be added to the resin, even up to 15%; this causes tensile properties to decrease drastically; it was found that the boards presented as conclusions of this study fail to meet the minimum quality standards for the market, therefore, this option is not viable at the industrial level.

SUMMARY OF THE INVENTION

[0071] The problem to be solved by the present invention, therefore, consists of providing an environmentally friendly alternative to formulations based on waxes derived from mineral oil or synthetic waxes, such as, for example, paraffin, which are obtainable from renewable resources instead of non-renewable resources. This is solved by the kinetically stable vegetable oil-based O/W formulations according to the invention, which comprise an O/W suspension containing hydrogenated or partially hydrogenated palm oil, soybean oil, low levels of surfactants and water, which can be manufactured at an industrial level, at reasonable cost levels and are useful for increasing the hydrophobicity of wood-based boards and stone wool or fiberglass insulation; they can be used, for example, in the manufacture of wood-based boards, fiber boards, agglomerates, compacted boards, oriented particle boards, stone wool or fiberglass insulation or combinations thereof. They can also be useful, in addition to increasing hydrophobicity, for example, as external and internal release formulations during the manufacture of the boards and insulations listed above or to reduce energy consumption in industrial refinement processes of lignocellulosic material. They have high kinetic stability and low viscosity.

[0072] Therefore, a first objective of the invention consists of a vegetable oil-based formulation, characterized by the fact that it is kinetically stable; wherein it comprises an oil-in-water (O/W) suspension, which comprises: - from 1% by weight to 5% by weight of surfactant, the surfactant being at least one anionic surfactant and at least one nonionic surfactant, the surfactant being added in this way or obtained in situ by adding between 1 and 2% by weight of an ethanolamine; - 15% by weight to 50% by weight of hydrogenated or partially hydrogenated palm oil; - from 0 to 25% by weight of paraffin; - from 2 to 8% by weight of soybean oil; and wherein: - the total amount of oils, being the sum of palm oil, paraffin and soybean oil in the O/W suspension does not exceed 55% by weight; - within the total amount of oils, 2 to 10% by weight is non-hydrogenated oil, and the rest is hydrogenated and/or partially hydrogenated oil; - the iodine value of the total quantity of oils is at least 10 g of iodine per 100 g of total quantity of oils; - the O/W suspension has a solids content of between 30% by weight and 55% by weight, and the rest of the suspension, until it reaches 100% by weight, is water, the solids content comprising all components that are different of water.

[0073] An additional objective of the invention consists of a method for obtaining an O/W suspension of the invention, as defined above, comprising: - adding a water phase to an oil phase, at least one of which contains a surfactant anionic or non-ionic, in such an amount to obtain a concentration of between about 1 wt % and about 5 wt % in the final emulsion, thus obtaining a W/O emulsion, until the W/O emulsion is inverted to a O/W emulsion; - heat the O/W emulsion to obtain a W/O emulsion; - cool the W/O emulsion to room temperature, to obtain the O/W suspension of the invention.

[0074] A further object of the invention consists in the use of an O/W formulation according to the present invention in the manufacture of wood-derived boards, fiberboards, particleboards, compacted boards, oriented particle boards, wood composite boards or stone wool or fiberglass insulation or combinations thereof.

[0075] The invention also relates to boards (wood-derived boards, fiberboards, agglomerates, compacted boards, oriented particle boards, wood composite boards) comprising a formulation as defined above additionally comprising up to 25% by weight of a formaldehyde sequestrant, which has a formaldehyde emission of 1 mg formaldehyde per square meter and hour, or below, as measured by the gas analysis method UNE-EN ISO 12460-3:2016.

[0076] The invention also relates to fiberglass insulations or stone wool insulations, comprising a formulation as defined above, additionally comprising up to 25% by weight of a formaldehyde scavenger, which has a formaldehyde emission of 1 mg of formaldehyde per square meter and hour, or below, as measured by the gas analysis method UNE-EN ISO 12460-3:2016.

DETAILED DESCRIPTION OF THE INVENTION

[0077] The present invention relates to kinetically stable vegetable oil-based formulations comprising an O/W suspension that contains water and hydrogenated or partially hydrogenated palm oil and soybean oil and that has low levels of surfactants, which can be manufactured on an industrial level and completely or partially avoids the use of non-renewable resources, e.g. petroleum-derived resources, e.g. paraffin. Due to their particular composition and average particle diameter, the formulations have high kinetic stability and low viscosity. Said formulations are useful for increasing the hydrophobicity of wood-derived boards or stone wool or fiberglass insulation; They can, therefore, be used in the manufacture of wood-based boards, wood composite boards, fiber boards (including MDF and HDF boards), chipboards, compacted boards, oriented particle boards, plywood, cardboards or insulation. stone wool or fiberglass or combinations thereof.

[0078] An emulsion, according to IUPAC, is a “fluid colloidal system in which liquid droplets and/or liquid crystals are dispersed in a liquid. The droplets often exceed general 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.”

[0079] On the other hand, a suspension, according to IUPAC, is “a liquid in which solid particles are dispersed”.

[0080] Although paraffin suspensions are often referred to as paraffin emulsions, in reality, they are suspensions, since the oil droplets in the aqueous phase, under normal temperature and pressure conditions, are in the solid state. Therefore, the correct term “suspension” will be used throughout this specification, specifically O/W suspension, as it comprises solid particles of oil and wax suspended in water. However, the formulations are such that they are liquid to allow for easy application.

[0081] Emulsifiers are a group of substances of different origins and properties that will contribute to greater stabilization of emulsions or suspensions; This is mainly due to its amphiphilic or double affinity character, which, from a physicochemical point of view, is defined as a nonpolar or doubly polar property. Within this large group of compounds it is possible to find, for example, surfactants.

[0082] Oils have the difficulty that they have the property of occluding water within their structure, normally between 2 and 6 times their weight. This property makes its emulsification very complicated, as it leads to the formation of semi-solid creams, which make it impossible for it to be properly applied to any material, for example, through spraying, which is the preferred form of application, for which the product needs to be in a liquid state. The high concentration of surfactants can help to emulsify such oils, however, the surfactants are, in part, hydrophilic and, therefore, a high amount of surfactant in the final suspension has the inconvenience of reducing the intrinsic hydrophobicity of the paraffin or other oil/wax used. to prepare the emulsion or suspension, since the surfactant, which is amphiphilic, has an affinity for water, thus making the formulations to which they are added less hydrophobic and, therefore, less efficient, showing greater swelling of the derived plates of wood to which they are applied. Therefore, as low a surfactant concentration as possible is desired.

[0083] Suspensions, so that they are useful for their intended uses, that is, improving water resistance and/or facilitating mold release and/or curing resins derived from formaldehyde and/or sequestering formaldehyde from resins derived from Formaldehyde in wood-based boards, fiberboards, particleboards, compacted boards, oriented particle boards, fiberglass or stone wool must comply with the following features: 1. High solids content: 45% to 60%. 2 .-Suspension stability of at least 1 month (kinetic stability) under normal conditions of temperature and pressure. 3 .-High performance as a hydrophobizing agent. 4.-Low level (below 15%) of surfactants. 5 .-Good compatibility with aminoplastic resins. 6.-Mechanical shear stability.

[0084] This was achieved by the O/W formulations of the present invention, which comprise an O/W suspension.

Definitions

[0085] Within the framework of the present invention, the following terms have the indicated meanings:

[0086] “Non-ionic surfactants” are surfactants that do not carry an electrical charge. Although they do not contain an ionic group as their hydrophilic component, hydrophilic properties are conferred on them by the presence of numerous oxygen atoms in a part of the molecule that are capable of forming hydrogen bonds with water molecules. For example, many long-chain alcohols exhibit some surfactant properties, such as fatty alcohols, cetyl alcohol, stearyl alcohol and cetostearyl alcohol, and oleyl alcohol. Other nonionic surfactants are alcohol ethoxylates, polyglycol ethers, polyoxyethylenealkyl ethers, secondary alcohol ethoxylates, polyoxyethylenealkyl ethers, polyalkylglycolakyl ethers (e.g., polyethylene and polypropylene glycolalkyl ethers), alkyl glycoside ethers, polyethyleneglycolalkylphenyl ethers or glycerolalkyl esters.

[0087] “Anionic surfactants” are surfactants that contain anionic functional groups in their head, such as sulfate, sulfonate, phosphate and carboxylates. Prominent alkyl sulfates include ammonium lauryl sulfate, sodium lauryl sulfate (sodium dodecyl sulfate, SLS, or SDS), and the related alkyl ether sulfates sodium lauryl sulfate (sodium lauryl ether sulfate). sodium or SLES) and sodium myride sulfate. Additionally, docusate (dioctyl sodium sulfosuccinate), perfluorooctanesulfonate (PFOS), perfluorobutanesulfonate, alkyl aryl ether phosphates, and alkyl ether phosphates are anionic surfactants.

[0088] The “Sauter mean diameter”, also designated as D(3,2), D32 or D(32) is the mean diameter with the same volume to surface area ratio as the integral set. It was originally developed by German scientist Josef Sauter in the late 1920s. The size of the droplets is determined based on the absorption/diffusion of light. The technique relies on the fact that absorption/diffusion is proportional to the surface area of the droplets.

[0089] The term “kinetically stable” within the framework of the present invention means that the formulations and suspensions to which the term refers do not form creams or separate into distinct phases within the indicated time interval, for example, at least 2 months.

[0090] “Normal temperature and pressure conditions” refers to a temperature of 20 °C and an absolute pressure of 1 atm.

[0091] “W/O emulsion” refers to a water-in-oil emulsion.

[0092] “O/W emulsion” refers to an oil-in-water emulsion.

[0093] “O/W suspension” refers to a suspension comprising solid particles of hydrogenated oil (wax) suspended in water.

[0094] “Hydrogenated oil” or “hydrogenated wax” within the framework of the present invention is intended to encompass any level or extent of hydrogenation, that is, it is intended to also include partially hydrogenated oil or wax; the term only excludes non-hydrogenated oil, that is, natural oil that has not been subjected to any type of hydrogenation.

[0095] “Formaldehyde-based resins” or “formaldehyde-derived resins”, as used within the scope of the present invention, refers to any resin or plastic that is produced from formaldehyde with other reactants, such as urea, phenol or melamine . For example, urea-formaldehyde resin is a non-transparent thermosetting or plastic resin produced from urea and formaldehyde. They are used in adhesives, finishes, chipboards, MDF and molded objects. Phenol formaldehyde resins (PF) or phenolic resins are synthetic polymers obtained by reacting phenol or phenol substituted with formaldehyde. They were widely used for the production of molded products including billiard balls, laboratory counters and as coatings and adhesives. Melamine formaldehyde resin is a rigid thermosetting plastic material produced from melamine and formaldehyde through polymerization. In its butylated form, it is dissolved in n-butanol and xylene. It is then used for crosslinking with alkyd, epoxy, acrylic and polyester resins, used in surface coatings. There are many types, ranging from very slow to very fast healing.

[0096] “Formaldehyde scavenger” in the context of the present invention refers to any compound that allows reducing the content of free formaldehyde in any product or composition. Any formaldehyde sequestrant known in the prior art can be used. For example, the formaldehyde scavenger may be selected from, but not limited to, urea, urea derivatives, hexamine, amino group containing compounds, hexamine, sulfite salts and metabisulfite salts.

[0097] “Catalyst for curing formaldehyde-based resins”, within the framework of the present invention, means any substance suitable for use to cure formaldehyde-based resins. The same may be selected from the group comprising ammonium bisulfite, ammonium nitrate and ammonium sulfate, but without limitations to said catalysts. Said catalysts are necessary to cure formaldehyde-based resins, which are generally used in the manufacture of all types of wood-based boards, fiberboards, particleboards, compacted boards, oriented particle boards and the like. If the formulations of the invention contain one or more catalysts, no additional catalysts or formulations containing catalysts are required to be used during the curing process.

[0098] “Wood composite boards” in the context of the present invention refers to boards obtained by agglutinating and compressing natural fibers, optionally in combination with synthetic fibers. Examples of the same, but without limitations, are agglomerates, fiber boards ( MDF and HDF), compacted boards, oriented particle boards and plywood.

[0099] “Synthetic fibers” in the context of the present invention refers to fibers made from polyester, polyethylene or polypropylene.

[0100] “Natural fibers” within the scope of the present invention refers to wood fibers, chips, particles, flakes or filaments and/or other natural fibers such as flax, hemp, rye straw, wheat straw, rice straw, stalks of hemp, kenaf stalks or sugar cane waste. Emulsification Process

[0101] The O/W suspensions according to the invention can be obtained through different emulsification methods, including emulsification methods well known in the art.

[0102] For example, O/W suspensions can be obtained by the direct emulsification method (sometimes referred to herein as the direct O/W method), through the slow addition of the oil phase to the aqueous phase, both heated to temperatures between about 60 and about 100 ° C, under stirring or equivalent mixing means, at rates between 100 and 10,000 rpm. The surfactant can be contained in the oil phase or in the aqueous phase, normally, but not necessarily, an ionic surfactant will be added to the aqueous phase and a non-ionic surfactant to the oil phase. Alternatively, the surfactant can be obtained in situ through the reaction of corresponding reactants.

[0103] O/W suspensions can also be obtained by the EIP (Emulsion Inversion Point) method (sometimes here called the EIP phase inversion method), sometimes also referred to as PIC (inversion concentration). phase), in which the aqueous phase is added to the oil phase, both heated to temperatures between about 60 and about 100 °C, therefore, in the first case, obtaining a W/O emulsion. Stirring or dispersing at rates between 100 and 10000 rpm are applied. When the additional aqueous phase is added, and the water/oil ratio increases in the system, the phases are reversed and an O/W suspension is obtained, having a particularly small particle (droplet) size, which is not dependent on the agitation factor. mechanics.

[0104] An additional emulsification method is a combination of two known phase inversion methods, namely EIP and PIT (Phase Inversion Temperature), which, to date, have only been used separately to prepare emulsions (sometimes , herein called the phase inversion method of combined EIP and PIT). This combined method comprises the steps of: - adding an aqueous phase to an oil phase, both heated to temperatures between about 60 and about 100 °C, under stirring or dispersing at rates between 100 and 10000 rpm, at least one of containing a non-ionic surfactant, in a certain amount to obtain a concentration between about 1% by weight and about 2% by weight in the final emulsion, thus obtaining a W/O emulsion, until the W/O emulsion be inverted to an O/W emulsion; - heat the O/W emulsion to at least 75 °C, until a W/O emulsion is obtained by phase inversion; - cool the W/O emulsion to room temperature to obtain an O/W suspension.

[0105] On the other hand, emulsification can be performed in a single reactor, using mechanical dispersion, a rotor-stator or with stirring and homogenizer.

[0106] Alternatively, emulsification can be carried out using two different reactors, an oil phase reactor and an aqueous phase reactor. The first reactor has a temperature regulation system and an agitator, while the second mixing reactor or reactor in addition to the temperature control system has a dispersant.

[0107] Emulsification can be carried out with stirring, mechanical stirring and dispersion, stirring and rotor-stator (for example, ULTRA TURRAX® type).

[0108] Various routes can be followed to prepare oil-in-water emulsions. The most obvious is to mix oil and water in the presence of a surfactant. The results depend strongly on the mixing conditions, such as mixing speed, temperature, type of oil, type of surfactant and quantities of each component used.

[0109] High energy dispersion methods comprise the stretching of droplets and the formation of hydrodynamic instability, through high shear, which is generated by a propeller or turbine mixers, thus producing thick emulsions (5- 100 microns); To further reduce the droplet size, a large amount of mechanical energy to increase the interfacial activity is required as the Laplace pressure increases as the droplet size decreases (Salager, J.L. et al. (2000), “Emulsion properties and related know-how to achieve them”, Pharmaceutical Emulsions and suspensions, F. Nielloud and G. Marti-Mestres Editores, Vol. 105, Drugs and Pharmaceutical Science, Marcel Dekker, New York, USA, chapter 3, pages 73 - 125).

[0110] The formation of an emulsion with an extremely small droplet size not only requires that the final system comply with certain composition and formulation variables, but the process through which the emulsion is obtained is also decisive.

[0111] Low methods are those in which the energy that is required to produce the emulsion is supplied from the transitions or phase changes that occur during the formation of emulsions (Salager, J.L. et al. (2004). “Using emulsion inversion in industrial processes”, Advances in Colloid and Interface science, vol. 108-109, 20, 259-272). This is possible by following three methods: transitional inversion, catastrophic inversion and phase inversion emulsification (Salager, J.L. et al. (2006), Emulsion Phase Inversion Phenomena, en: “Emulsions and Emulsion Stability”, J. Sjoblom Editor, 2nd Edition , Marcel Dekker, New York, USA, pages 185-226.).

[0112] Transitional inversion includes the phase inversion temperature method, PIT method (Shinoda, H., et al. (1968), “The effect of temperature on the phase equilibria and the types of dispersion of the ternary system composed of water, cyclohexane, and non-ionic surfactant”. J. Colloid Interface Sci. 26, 70-74.), which is widely used in industry and which is based on the formation of emulsion using a sudden change in temperature . However, its use is limited to systems that are formulated with non-ionic surfactants of the ethoxylated type, which alter their hydrophilic-lipophilic balance with temperature: at temperatures below the phase inversion temperature, oil-in-water emulsions are formed, while, at temperatures above said temperature, water-in-oil emulsions are formed.

[0113] Catastrophic inversion occurs when the concentration of the internal phase in a surfactant/water/oil system is very high, generating the formation of a multiple emulsion, as the system is not capable of solubilizing a greater amount of phase dispersed within of the drops. This can be accomplished in two ways, from the normal side of the emulsion to the abnormal side, when the amount of internal phase or the abnormal side of the emulsion is increased to the normal side.

[0114] This is the beginning of the emulsification method initially called emulsion inversion point (EIP) described by Marszall (1976) (Marszall, L. (1976), “Adsorption of nonionic surfactants at the oil-water interface and emulsion inversion point”. Colloid Polymer Sci. 254, 674-675), used by Lin (1978) (Lin, T.J. (1978), “Low-energy emulsification I: principles and applications”. J soc. Cosmet. Chem 29, 117 -125) and improved by Sagitani (1992) (Sagitani, H (1992), Phase-inversion and D-Phase Emulsification, “Organized Solutions”, S.E. Friberg y Lindman B., Editors, Marcel Dekker, New York), and also known as phase inversion concentration (PIC).

[0115] In the case of obtaining oil-in-water (O/W) emulsions, the method consists of adding water to a dispersion formed by oil and surfactant, until the final emulsion is formed. By increasing the water content in the initial system, transitions or inversion of microemulsion phases and/or lamellar liquid crystals occur, for the formation of nanoemulsions through phase transition methods (Forgiarini, A. (2001). “Estudio of the relationship between phase behavior and formation of aqueous external phase nano-emulsions”, PhD Thesis, Chemical Engineering and Metallurgy, University of Barcelona, Spain; Morales, D. et al., “A study of the relationship between bicontinuous microemulsions and oil/water nanoemulsion formation”, Langmuir 19 (2003), 7196-7200).

Formulations of the invention

[0116] The present invention refers, in a first objective, to a formulation based on vegetable oil, which is characterized by the fact that it is kinetically stable; wherein it comprises an oil-in-water (O/W) suspension, which comprises: - from 1% by weight to 5% by weight of surfactant, the surfactant being at least one anionic surfactant and at least one nonionic surfactant, the surfactant being added in this way or obtained in situ by adding between 1 and 2% by weight of an ethanolamine; - 15% by weight to 50% by weight of hydrogenated or partially hydrogenated palm oil; - from 0 to 25% by weight of paraffin; - from 2 to 8% by weight of soybean oil; and wherein: - the total amount of oils, being the sum of palm oil, paraffin and soybean oil in the O/W suspension does not exceed 55% by weight; - within the total amount of oils, from 2 to about 10% by weight is non-hydrogenated oil, and the rest is hydrogenated and/or partially hydrogenated oil; - the iodine value of the total quantity of oils is at least 10 g of iodine per 100 g of total quantity of oils; - the O/W suspension has a solids content of between 30% by weight and 55% by weight, and the rest of the suspension, until it reaches 100% by weight, is water, the solids content comprising all components that are different of water.

[0117] It was surprisingly found that, if the iodine value of the total amount of oils in the formulation is above 10 g of iodine per 100 g of the total amount of oils, the suspensions and, therefore, the formulations obtained with them are kinetically much more stable than if the iodine value is below 10, as will be shown in the Examples, without compromising the waterproofing or hydrophobic effect of the formulations. According to the prior art, it was believed that hydrogenated oils had a superior hydrophobic effect, and thus a high hydrogenation effect was intended.

[0118] In some embodiments, the soybean oil in the formulation is non-hydrogenated soybean oil, which has an iodine value in the range of 120 to 155 grams of iodine per 100 grams of soybean oil.

[0119] The palm oil in the formulation is hydrogenated or partially hydrogenated palm oil. The amount of palm oil and non-hydrogenated soybean oil, which has an iodine value in the range of 120 to 155 grams of iodine per 100 grams of soybean oil, can be adjusted within the defined weight percentages, so that the iodine value of the total amount of oils is above 10 g of iodine per 100 g of the total amount of oils. The respective required amounts can be easily calculated based on the iodine values of the individual oils.

[0120] According to some embodiments, the vegetable oil-based formulation of the invention as defined above may comprise up to 25% of a formaldehyde sequestrant, relative to the total weight of the formulation. This can be useful when the formulation is used to manufacture boards or insulation using formaldehyde-based resins; however, the presence of formaldehyde sequestrant for other manufacturing is not harmful. In any case, if the formulation according to the invention comprises a sufficient amount of formaldehyde scavenger, during the manufacture of the boards or insulation, conveniently, no addition of additional formaldehyde scavengers is necessary to reduce formaldehyde emissions to the required standards. .

[0121] According to some embodiments, the vegetable oil-based formulation of the invention as defined above may comprise up to 25% of a catalyst for curing formaldehyde-derived resins, relative to the total weight of the formulation. This can be useful when the formulation is used to manufacture boards and insulation using formaldehyde-based resins; however, the presence of a catalyst for other manufacturing is not harmful. In any case, if the formulation according to the invention comprises a sufficient amount of catalyst to cure formaldehyde-derived resins during the manufacture of the boards or insulations, conveniently no addition of catalysts is necessary to cure the resins.

[0122] According to some embodiments, the solids content is between about 45% by weight and about 55% by weight. Solids content refers to the sum of all components of the formulation that are other than water.

[0123] The formulations according to the invention are kinetically stable, which means that the formulations and suspensions to which the term refers do not form creams nor separate into distinct phases within the indicated time interval, for example, solid particles do not appear throughout the formulation within a time interval. According to some embodiments, the formulation of the invention is kinetically stable for at least 2 months under normal temperature and pressure conditions, preferably at least 3 months, more preferably at least 4 months, even more preferably at least 6 months, even more preferably at least 1 year and most preferably at least 2 years. This stability allows the formulation to be commercially distributed and offered without the need for special conditions or equipment.

[0124] The time interval of kinetic stability can be further increased to at least two years, by reducing the storage temperature, for example, to temperatures between 5 °C and 15 °C, preferably between 5 °C and 10°C.

[0125] According to some embodiments, the O/W suspension comprised in the formulation of the invention may contain up to 25% by weight of paraffin. Paraffin is the state of the art standard for increasing the hydrophobicity of plates or insulation and can be included to an extent in the formulations of the invention. The paraffin that may be contained in the formulations may be paraffin corresponding to CAS No. 800274-2 or crude wax (petroleum), for example, as corresponding to CAS No. 64742-61-6.

[0126] It was found that the presence of soybean oil in the formulation reduces the initial melting point of hydrogenated or partially hydrogenated palm oil and surprisingly appears to contribute to increasing the stability of the emulsion. Non-hydrogenated soybean oil has an iodine value of 120 to 155 g of iodine per 100 g of oil.

[0127] According to some embodiments, the formulation of the invention contains from 4 to 8% by weight of soybean oil.

[0128] According to some embodiments, the formulation of the invention may contain up to about 25% by weight of paraffin and 2 to 8% by weight of soybean oil.

[0129] Within the O/W suspension, preferably at least one of the palm oil or soybean oil consists of hydrogenated or partially hydrogenated oils.

[0130] In embodiments in which the O/W suspension contains paraffin, the oil particles in the suspension have a Sauter average diameter between about 0.3 and about 10 micrometers, preferably between about 0.3 and about 4 micrometers, more preferably between about 0.3 and about 2 micrometers.

[0131] In embodiments in which no paraffin is present, i.e., in which the paraffin content in the O/W suspension is 0%, the oil particles in the suspension have a mean Sauter diameter between about 2 and about 10 micrometers, preferably between about 3 and about 9, more preferably between about 4 and about 8 micrometers, even more preferably between about 4 and about 7 micrometers, and most preferably between about 4 and about 6 micrometers.

[0132] In the formulation of the invention, preferably at least about 50% by weight of the fatty acids in the total amount of oil are fatty acids that have 20 to 22 carbon atoms. In the case where insufficient fatty acids of said length are contained in the oils used as raw materials, fatty acids having 20 to 22 carbon atoms can be added to the formulation, until the indicated percentage is reached.

[0133] In the formulation of the invention, the surfactant is a mixture of at least one nonionic surfactant and at least one anionic surfactant. Surfactants can be added to the water or oil phase, or obtained in situ, within the aqueous phase, by a saponification reaction. The weight percentages indicated refer to the final concentration of surfactants within the O/W suspension, regardless of whether they were added as such or generated in situ through the reaction of fatty acids contained in the oils or waxes and an ethanolamine that is added to the phase aqueous solution, before carrying out the emulsification. When adding the aqueous phase to the oil phase or vice versa, ethanolamine will react with fatty acids from the oil phase and generate a surfactant in situ. Ethanolamine can be selected, for example, but without limitation, from monoethanolamine, diethanolamine and triethanolamine.

[0134] Saponification of fats and oils is the most widely used soap-making process. This method involves heating fats and oils and reacting them with an alkaline liquid to produce soap and water (pure soap) plus glycerin.

[0135] The other main soap making process is the neutralization of fatty acids with an alkali. Fats and oils are hydrolyzed (split) with high-pressure steam to yield crude fatty acids and glycerin. The fatty acids are then purified by distillation and neutralized with an alkali to produce soap and water (pure soap).

[0136] When the alkali is an amine, for example, monoethanolamine or diethanolamine, an amine soap is formed.

[0137] Generally, amine soaps are formed "in situ" by direct reaction of suitable amounts of amine and fatty acid.

[0138] The carboxylate end of the soap molecule is attracted to water. This is called the hydrophilic end (attracted to water). The hydrocarbon chain is attracted to oil and grease and repelled by water. It is known as the hydrophobic end (not attracted to water).

[0139] In some embodiments, the surfactant is selected from secondary alcohol ethoxylate and fatty alcohol ethoxylate.

[0140] In the formulation of the invention, the ratio of surfactant versus the total amount of oil, generally known as the S/O ratio, in the O/W suspension, preferably is between about 4% by weight and about 15% by weight , more preferably between about 4% by weight and about 12% by weight, even more preferably between about 4% by weight and about 8% by weight, most preferably between about 4% by weight and about 6% by weight. % by weight.

[0141] According to some embodiments, the formulation may contain up to 25% of a catalyst for curing formaldehyde-based resins; said catalyst, within the framework of the present invention, means any substance suitable for use to cure formaldehyde-based resins. It can be selected from the group comprising bisulphited ammonium, ammonium nitrate and ammonium sulfate, but without limitations to said catalysts. Said catalysts are necessary to cure formaldehyde-based resins, which are generally used in the manufacture of all types of wood-based boards, fiberboards, particleboards, compacted boards, oriented particle boards and the like. If the formulations of the invention contain one or more catalysts, no additional catalysts or formulations containing catalysts are required to be used during the curing process.

[0142] That is, the present invention also refers to formulations comprising from 75 to 100% of the O/W suspensions of the present invention and additionally up to 25% by weight of at least one catalyst for curing formaldehyde-derived resins. Thus, the catalyst for curing formaldehyde-derived resins can be a single catalyst or a mixture of catalysts. Preferably, the catalyst is selected from ammonium bisulfite, ammonium nitrate and ammonium sulfate. That is, the formulations of the present invention may comprise a suspension according to the present invention and a catalyst for curing formaldehyde-derived resins or emulsion formulation according to the present invention and two different catalysts for curing formaldehyde-derived resins, or a suspension according to the present invention and three different catalysts for curing resins derived from formaldehyde among others. For example, the formulations may comprise the suspension according to the present invention and ammonium bisulfite; or the suspension according to the present invention and ammonium nitrate; or the suspension according to the present invention and ammonium sulfate; or the suspension according to the present invention and ammonium bisulfite and ammonium nitrate; or the suspension according to the present invention and ammonium nitrate and ammonium sulfate; or the suspension according to the present invention and ammonium bisulfite and ammonium nitrate and ammonium sulfate. That is, all possible combinations are included within the scope of the present invention.

[0143] According to some embodiments, the formulation of the invention may contain up to 25% of a formaldehyde scavenger, to sequester excess formaldehyde in formaldehyde-based resins, typically the formaldehyde scavengers used are urea, monoethanolamine and diethanolamine, however, other formaldehyde scavengers can be used in the formulations of the invention.

[0144] Therefore, the present invention also refers to formulations comprising from 75 to 100% of the O/W suspension according to the present invention, and additionally up to 25% by weight of at least one formaldehyde sequestrant. Thus, the formaldehyde scavenger can be a single compound or a mixture of compounds. Preferably, the formaldehyde scavenger is selected from urea, monoethanolamine and diethanolamine. That is, the formulations of the present invention may comprise a suspension according to the present invention and a formaldehyde sequestrant or a suspension according to the present invention and two different formaldehyde sequestrants or a suspension according to the present invention and three sequestrants. of different formaldehyde, among others. For example, the formulations may comprise the suspension according to the present invention and urea; the suspension according to the present invention is monoethanolamine; or the suspension according to the present invention and diethanolamine; or the suspension according to the present invention is urea and monoethanolamine; or the suspension according to the present invention is urea and diethanolamine; or the suspension according to the present invention is monoethanolamine and diethanolamine; or the suspension according to the present invention is urea and monoethanolamine and diethanolamine. That is, all possible combinations are included within the scope of the present invention.

[0145] The invention also relates to formulations comprising from 50 to 100% of the suspensions according to the present invention, and additionally up to 25% by weight of at least one formaldehyde sequestrant, and up to 25% by weight of at least a catalyst for curing formaldehyde-derived resins. That is, the formulations may comprise the suspension according to the present invention and a formaldehyde sequestrant and a catalyst for curing formaldehyde-derived resins; or the suspension according to the present invention and a formaldehyde scavenger and two catalysts for curing formaldehyde-derived resins; or the suspension according to the present invention and a formaldehyde scavenger and three catalysts for curing formaldehyde-derived resins; or the suspension according to the present invention and two formaldehyde scavengers and a catalyst for curing formaldehyde-derived resins; or the suspension according to the present invention and three formaldehyde scavengers and a catalyst for curing formaldehyde-derived resins; or the suspension according to the present invention and two formaldehyde scavengers and two catalysts for curing formaldehyde-derived resins; or the suspension according to the present invention and two formaldehyde scavengers and three catalysts for curing formaldehyde-derived resins; or the suspension according to the present invention and three formaldehyde scavengers and a catalyst for curing formaldehyde-derived resins; and so on, all types of combinations being included within the scope of the present invention. Preferably, the catalyst is selected from ammonium bisulfite, ammonium nitrate and ammonium sulfate. Preferably, the formaldehyde scavenger is selected from urea, monoethanolamine and diethanolamine.

[0146] These formulations allow, simultaneously, to improve water resistance and facilitate mold release and/or cure formaldehyde-derived resins and/or sequester formaldehyde from formaldehyde-derived resins, without the need to add additional products to achieve the said results of the final products to which they are applied. For example, if the formulation contains a formaldehyde scavenger, no other formaldehyde scavenging product is normally required; or if the formulation contains a catalyst for curing formaldehyde-derived resins, no other catalyst product is normally required; and so on.

[0147] Formaldehyde sequestrants and catalysts for formaldehyde-derived resins will be incorporated into the suspensions through two preferred methods: A) They are solubilized in the aqueous phase before starting the emulsification process. B) They will be incorporated through agitation and/or mechanical dispersion in a finished suspension as defined above, in accordance with the invention.

[0148] Other additives can be added to the formulations, such as, for example, one or more of biocides or adjuvants and process additives, such as rheological agents, antifoaming agents, stabilizers, appearance modifiers, thickeners, gelling agents, viscosifying agents or of texture, fluidizing agents, diluents and fillers.

[0149] Rheological agents are an important category of process additives, whose function is to act on the fluid mechanical behavior of liquid compounds or powders. Since they facilitate or inhibit displacement and depending on the field of application, they are sometimes also called thickeners, gelling agents, viscosifying or texture agents or fluidizing agents.

[0150] Stabilizers include a wide variety of reagents that prevent degradation of product quality over time under the influence of physicochemical (sedimentation, flocculation), chemical (oxidation, photodegradation) or biological (microbial attack) phenomena.

[0151] Appearance modifiers are similar to previous additives in that they act in another sense, on appearance. They include different compounds capable of interacting with light such as opaque white pigments, black and colored pigments, pearlescent, fluorescent or phosphorescent compounds and agents that produce a matte appearance.

[0152] Process additives combine a wide range of compounds as they include all formulation aids that facilitate product preparation operations and application.

[0153] Diluents and fillers can fall into this category although they do not play any role in the effectiveness of the formula. In fact, they are often introduced into the formula to reduce its cost and increase its volume or weight. In reality, they are important as they serve as the matrix for the active compounds and, thus, facilitate their manipulation by ensuring the cohesion of the powders and reducing the viscosity of liquid formulas. They are distinguished from other adjuvants by two features: they are cheap and they are incorporated into the formula in high proportions.

[0154] Some commercial additives that can be used and have been tested within the framework of the present invention are, as an illustrative example:

[0155] Biocides: Mergal® 758, Acticide® MBS, Mirecide® M / 85.

[0156] Antifoam agents: BYK® 037, BIY® 12, Foammaster® MO NXZ, Contrapen® PR 194, Mergal® 758, Mergal® V684k, Mergal® 721K3.

Industrial applications

[0157] The formulations of the present invention can be applied to a variety of products to increase their hydrophobicity, that is, to improve their water resistance, mainly to all types of hydrophilic materials, mainly materials comprising cellulosic fibers, wood fibers or vegetable, such as items obtained from solid wood or composites comprising cellulosic fibers, for example, filaments, particles, fibers and chips from wood or other vegetable sources, such as rye straw, wheat straw, rice straw, stalks hemp, kenaf stalks or sugar cane waste, optionally combined with synthetic fibers. Such hydrophilic materials comprising cellulosic fibers include, but are not limited to, solid wood boards, microlaminated wood boards (LVL), plywood boards, oriented particle boards (OSB), resin-based particleboards, cement-based particleboards, fiberboards (including MDF and HDF), wood-plastic composites (WPCs), which are hydrophilic materials produced from wood fiber and/or wood flour and thermoplastics (or thermoplastics) such as polyethylene, polypropylene, polyvinyl chloride and wood composites manufactured with inorganic binders such as gypsum, Portland cement or magnesia cement, containing between 10 and 70% by weight of wood particles. The formulations can also be used to increase the hydrophobicity of fiberglass insulation and stone wool insulation.

[0158] The formulations improve the water repellent properties of the materials to which they are applied, that is, water resistance, especially by reducing the swelling of materials when exposed to water and also the absorbance of water.

[0159] An object of the invention is the use of a formulation according to the present invention in the manufacture of articles selected from wood-derived boards, wood composite boards, fiberboards, particleboards, compacted boards, oriented particle boards , plywood, cardboard, stone wool or fiberglass insulation or combinations thereof.

[0160] The aforementioned use will increase the hydrophobicity of manufactured articles, namely, wood-based boards, wood composite boards, fiber boards, agglomerates, compacted boards, oriented particle boards, plywood, cardboard, stone wool or fiberglass insulation, manufactured with the formulations according to the invention.

[0161] Articles can be manufactured using a formaldehyde-based resin to achieve cohesion of fibers, particles, chips, etc.

[0162] In this case, the use of the formulation according to the invention, additionally comprising up to 25% by weight of at least one formaldehyde sequestrant, additionally reduces free formaldehyde in the manufactured articles, that is, reduces the emission of formaldehyde from the articles manufactured.

[0163] In some embodiments, said formaldehyde emission is reduced to 1 mg of formaldehyde per square meter and hour, or below, as measured by the gas analysis method UNE-EN ISO 12460-3:2016.

[0164] The formulations may also be useful as internal mold release formulations. The formulations, for example, can be used in the manufacture of molded items, such as plates or panels, to prevent the adhesion of fibers or chips, bonded with synthetic resins, to the metal parts of the processes, thus reducing the degree of soiling of the material. manufacturing process.

[0165] The formulations may also be useful as external mold release formulations. The formulations, for example, can be applied to the surface of the layers or interposed with fibers and/or chips and/or particles and/or glass fiber or stone wool, for example, but without limitation, by spraying, before being pressed in a press, during the manufacture of cellulose-derived boards, wood-derived boards, fiberboards, agglomerates, compacted boards, oriented particle boards, fiberglass or stone wool or combinations thereof.

[0166] The formulations of the present invention also provide, in addition to improving various features of the final products, as indicated above, the technical advantage of reducing energy consumption, both during the preparation of the suspension and formulation, compared to emulsions based on of paraffin of the state of the art and during its application.

[0167] This energy saving is based on the fact that no homogenizer is used in the emulsification process through low mechanical energy, thus saving at least approximately 10 kWh per ton of suspension manufactured. The mechanical energy required in the emulsification process is reduced by more than 50%.

[0168] When carrying out the industrial refining process of lignocellulosic material (for example, but without limitation, MDF or paper pulp) with the use of the formulations of the invention, compared to the use of traditional paraffin suspensions, a reduction of about 15-20% energy consumption is detected, for example a reduction from 140 kWh/tn of refined dry pine wood when using traditional paraffin suspensions, to 115 kWh/tn of refined dry pine wood when using the formulations according to the present invention, has been observed.

[0169] Therefore, an additional aspect of the invention consists of an industrial refining process of lignocellulosic material, characterized by the use of formulations according to the present invention. In a particular embodiment, said industrial refining process has an energy consumption that is reduced by more than 10% compared to an industrial refining process of lignocellulosic material using paraffin suspensions according to the state of the art, preferably more than 15%, more preferably between 15 and 20%.

[0170] As a particular embodiment, the fiberboards may be a board manufactured by the use of lignocellulosic fibers with the use of heat and/or pressure, in accordance with the EN 316 standard. Yet another embodiment of a fiberboard, a rigid fiber board as defined in standard EN316, manufactured from lignocellulosic fibers through the “wet process”, i.e. with a water content of the fibers, when processed into the board, of 20% or more, having a density of 900 kg/m3 or more. As a particular embodiment, resin bonding is manufactured by applying heat and pressure to wood particles (chips, particles, sawdust, scrapings and the like) and/or other lignocellulosic materials in particle form (hemp fibers, flax , bagasse and similar), through the addition of a binder, in accordance with the EN 309 standard. As a particular modality, oriented particle board (OSB) is made up of several layers of wood chips, of a certain shape and thickness, under the addition of a binder, in accordance with EN 300.

[0171] When the formulations additionally comprise at least one formaldehyde resin and at least one catalyst for curing the formaldehyde-based resins, and are applied in the manufacture of panels or boards derived from wood, panels or boards can be obtained that comply with European standards, without the need for additional compounds or products and even be classified as E1 according to the EN 120 standard, in relation to their formaldehyde content or even achieve a CARB II classification, according to the ASTM standard E 1333.

[0172] Thus, another object of the invention are boards (wood-derived boards, wood composite boards, fiber boards, agglomerates, compacted boards, plywood, cardboards, oriented particle boards) obtained with the use of a resin derived from formaldehyde and the formulation of the invention further comprising a formaldehyde scavenger, which has a formaldehyde emission of 1 mg formaldehyde per square meter and hour, or below, as measured by the UNE-EN ISO 12460-3 gas analysis method: 2016.

[0173] The formulations of the invention can also be applied to stone wool or fiberglass insulation to improve their water resistance and, if the formulations comprise, in addition to the suspension, at least one catalyst for curing formaldehyde-based resins, They also act as a catalyst formulation to cure formaldehyde-derived resins from stone wool or fiberglass insulation. Or, if the formulations comprise, in addition to the suspension, at least one formaldehyde scavenger, they also act as a formulation for scavenging excess formaldehyde.

[0174] Another object of the invention, therefore, is fiberglass or stone wool insulation, obtained with the use of a resin derived from formaldehyde and the formulation of the invention which additionally comprises a formaldehyde sequestrant, having an emission of formaldehyde of 1 mg formaldehyde per square meter and hour, or below, as measured using the gas analysis method UNE-EN ISO 12460-3:2016.

[0175] The present invention, therefore, relates to the use of a formulation according to the invention to improve the water resistance of wood-based boards, wood composite boards, fiber boards, agglomerates, compacted boards , oriented particle boards, plywood, cardboard or stone wool or fiberglass insulation. The present invention also relates to wood-based boards, wood composite boards, fiber boards, agglomerates, compacted boards, oriented particle boards, plywood, cardboard or stone wool or fiber wool insulation. fiberglass obtained by using the formulations of the invention.

[0176] A further object of the invention is the use of an O/W formulation according to the present invention in the manufacture of wood-based boards, wood composite boards, fiberboards, particleboards, compacted boards, oriented particle boards, plywood , cardboard or stone wool or fiberglass insulation or combinations thereof. The present invention also relates to wood-based boards, fiberboards, agglomerates, compacted boards, oriented particle boards, boards or other insulation articles produced from fiberglass or stone wool, or combinations thereof, obtained through the use of the formulations of the invention.

[0177] The present invention also relates to the use of a formulation according to the invention, as an internal mold release formulation in the manufacture of wood-based boards, wood composite boards, fiber boards, particleboards, of compacted boards, oriented particle boards, plywood, cardboard or stone wool or fiberglass insulation or combinations thereof. Therefore, the formulations can be used, for example, to reduce or prevent the adhesion of fibers, chips or particles, bonded with synthetic resins, to the metal parts of the manufacturing process, reducing the degree of contamination of the manufacturing process. The present invention also relates to wood-based boards, wood composite boards, fiber boards, agglomerates, compacted boards, oriented particle boards, plywood, cardboard or stone wool or fiber wool insulation. glass fiber or combinations thereof, obtained through the use of the formulations of the invention.

[0178] Furthermore, the invention relates to the use of a formulation according to the invention, as an external mold release formulation for application to layers or interpositions of fibers and/or chips and/or particles and/or fiberglass. glass or stone wool, before being pressed in a press, in the manufacture of wood-based boards, wood composite boards, fiber boards, particleboards, compacted boards, oriented particle boards, plywood, cardboard or stone wool or fiberglass insulation, or combinations thereof. Therefore, the formulations can be used, for example, to reduce or prevent adhesion of panels or plates for the manufacturing process. The present invention also relates to wood-based boards, wood composite boards, fiber boards, agglomerates, compacted boards, oriented particle boards, plywood, cardboard or stone wool or fiber wool insulation. fiberglass or combinations thereof, obtained through said use.

MDF board manufacturing

[0179] The Composite Panel Association defines medium density fiberboard (MDF) as a dry-formed panel product manufactured from lignocellulosic fibers combined with a synthetic resin or other suitable binder. The panels are compressed to a density of 496 to 801 kilograms per cubic meter (kg/m3) in a hot press. The entire interfiber bond is formed by a synthetic resin or other suitable organic binder.

[0180] MDF has a more uniform density across the board and has tight, smooth edges that can be machined. It can be finished to a smooth surface and printed with grain, eliminating the need for veneers and laminates. Most thicker MDF panels are used as core material in furniture panels. Medium density fiberboard panels thinner than 1/2 inch are typically used for the sides.

[0181] The general steps used to produce MDF include mechanically pulping wood chips into fibers (refining), drying, blending fibers with resin and sometimes wax, turning the resined material into a mat and hot pressing .

[0182] Equipment for MDF typically consists of wood chips. Wood chips typically are delivered by truck or rail from distant locations such as sawmills, plywood mills, furniture manufacturing facilities, talisk mills and whole tree chipping operations. If the wood chips are prepared locally, the logs are peeled, cut to more manageable lengths, and then sent to crushers. If necessary, the chips are washed to remove dirt and other debris.

[0183] The cleaned chips are softened in a pressurized digester with steam, then transported into a pressurized refinery chamber. In the refinery chamber, single or double revolution discs are used to mechanically pulp the softened chips into fibers suitable for producing board.

[0184] From the refineries, the fibers move to the drying and blending area. A rotary pre-dryer can be used for initial drying of relatively damp furniture. Regardless of whether or not a predryer is used, tube dryers are typically used to reduce the hydration content of fibers to desired levels. Single-stage or multi-stage tube drying systems are commonly used in MDF manufacturing. Most multistage tube drying systems incorporate two stages. In multistage tube dryers, there is a primary tube dryer and a second stage tube dryer in series separated by an emission point such as a cyclonic collector. Heat is generally supplied to tube dryers by direct burning of propane, natural gas, or distilled oil or by indirect heating.

[0185] The sequence of drying and blending operations depends on the method by which resins and other additives are blended with the fibers. Urea-formaldehyde (UF) resins are the most common resins used in the manufacture of MDF. Phenolic resins, melamine resins and isocyanates are also used. Some plants inject resins into a short hold blender, while most facilities inject resin formulations into a blow line system. If the resin is added in a separate blender, the fibers are first dried and separated from the gas stream by a fiber recovery cyclone, then transported to the blender. The fibers are then mixed with the resin, wax and any other additives and transported to a dry fiber storage box.

[0186] If a blow line system is used, the fibers are first mixed with resin, wax and other additives in a blow line, which is a duct that discharges the resined fibers to the dryer. After drying, the fibers are separated from the gas stream by a fiber recovery cyclone and then transported to a dry fiber storage bin.

[0187] Air transports the resin fibers from the dry storage box to the forming machine, where they are deposited on a continuously moving screen system. The continuously formed mat must be pre-pressed before being loaded into the hot press. After pre-pressing, a pre-trimming is carried out. The trimmed material is collected and recycled to the forming machine.

[0188] The pre-pressed and trimmed mats are then transferred to the hot press. The press applies heat and pressure to activate the resin and bind the fibers into a solid panel. The mat may be pressed in a continuous heat press, or the pre-compressed mat may be cut by an overhead cutting saw into individual mats which are then loaded into a multi-opening batch type hot press. Steam or hot oil heating of the press plate glass is common in domestic MDF mills. After pressing, the boards are cooled, sanded, trimmed and sawn to final dimensions. The boards can also be painted or laminated. Finally, the finished product is packaged for shipping.

[0189] The formulations of the invention can be used in the manufacture of MDF boards, both to increase their hydrophobicity and to reduce their adhesion to equipment during manufacturing.

BRIEF DESCRIPTION OF FIGURES

[0190] Figures 1 a) and b) show representative SEM images corresponding to the FORESA WAX 2102 sample. As can be seen, the sample is homogeneously distributed on the surface of the glass slide on which it was deposited, starting the formation of a film ( Figure a)). In some parts of the sample, it is possible to observe some spherical morphology that could be due to the formation of particles before their coalescence as a film (Figure b)).

[0191] Figures 2 a) and b) show representative SEM images corresponding to sample S21 of Example 5. As can be seen, the sample consists of well-separated spheres that exhibit high polydispersity.

[0192] Figure 3 graphically represents the viscosity measured at different shear rates for the formulation according to invention S21 at different dates (reflected by different formats).

[0193] Figure 4 shows a graph of the Sauter diameter distribution of the particles, at different points in time: weeks 0, 1, 2, 3 and 4, for formulation S8.

EXAMPLES

[0194] In the following, the invention will be further illustrated by means of Examples and Comparative Example. The Examples should in no case be construed as limiting the scope of the invention, but only as an illustration of the invention.

[0195] Throughout the Examples, the kinetically stable vegetable oil-based formulations of the invention are repeatedly compared with commercial paraffin suspensions, which correspond to the generally used prior art standard. They are available to the public from the Spanish company FORESA, S.A. (http://www.foresa.com/en), offered under the names FORESA WAX 2102 (the European UFI (https://poisoncentres.echa.europa. eu/es/ufi-generator) for this suspension is currently 30001013/1) and FORESA WAX 1102 (the European UFI (https://poisoncentres.echa.europa.eu/es/ufi-generator) for this suspension is currently 30001399 /1).

[0196] FORESA WAX 2102 contains a combination of two types of paraffin, namely about 45% by weight of a paraffin with a low oil content (oil content below 6% by weight, melting point 49-58 °C) and about 11% of a paraffin with a high oil content (maximum oil content 12% by weight, melting point 42-53°C), has a solids content of 58-62% by weight weight and a pH at 25 °C between 8.5 and 10.5.

[0197] FORESA WAX 1102 contains only paraffin with a high oil content (oil content between 6 and 12% by weight, melting point of 42-53 °C), has a solids content between 58 and 62% by weight and a pH at 25 °C between 8.5 and 10.5.

Example 1: Formulation preparation

[0198] Several formulations were prepared.

[0199] Some were prepared by direct O/W emulsion, others using the EIP phase inversion method, others using a combined EIP and PIT method. The methods were explained above.

[0200] In TABLE 1 (see below), a list of some of the prepared formulations is shown, detailing the weight percentage of the individual components, the saturation level of the palm oil used (by indicating the iodine value) and the type of surfactant used. Furthermore, the emulsification method is indicated: a: Direct O/W method b: EIP method c: Combined EIP and PIT method

[0201] In an additional column, the mean particle Sauter diameter is indicated. All formulations obtained had a stability of at least 2 months under normal temperature and pressure conditions (i.e., a temperature of about 20 °C and an absolute pressure of about 1 atm).

[0202] Those formulations having an iodine value of the total amount of oil above 10 grams of I2 per 100 grams of total oil are in accordance with the present invention.

Example 2: detailed preparation of an emulsion or suspension according to the invention via the direct O/W method: S6 (see TABLE 1)

[0203] 20 grams of BE-30 paraffin, 180 grams of hydrogenated palm wax, which has an iodine value < 10 grams of I2/100 grams and 5 grams of Tergitol® 15-S were mixed, introduced into a reactor oil phase and heated to approximately 70 °C. 275 grams of water were introduced into an aqueous phase reactor and heated to about 70 °C. The oil phase was slowly added to the aqueous phase at a rate of 20 grams/min. The mixture was mixed at a stirring rate of 450 rpm. Subsequently, the mixture was cooled at a rate of 4.5 °C per minute until it reached a temperature of 20-25 °C. Almost 500 grams of a liquid suspension were obtained, having a pH value of about 10 and about 45% solids. The suspension was kinetically stable for at least 3 months under normal pressure and temperature conditions.

Example 3: Detailed preparation of an emulsion or suspension according to the invention via the direct O/W method: S9 (see TABLE 1)

[0204] 200 grams of molten hydrogenated palm wax, having an iodine value < 10 grams of I2/100 grams, was introduced into an oil phase reactor, 7 g of long chain fatty acid added and heated to about 70 °C under stirring at about 1,000 rpm. 275 grams of water were introduced into an aqueous phase reactor and 10 grams of diethanolamine were added to obtain the anionic surfactant in situ, through reaction with fatty acids; and the reactor contents were heated to about 70°C. The oil phase was slowly added to the aqueous phase at a rate of 14 grams/min, with a dispersion rate of 150 rpm. Once the addition is complete, 5 grams of a nonionic surfactant, a secondary alcohol ethoxylate, e.g. Tergitol 15-S-9, is added. The reaction of diethanolamine and fatty acids to obtain an anionic surfactant has already occurred. The mixture was stirred for 16 min. Subsequently, the mixture was cooled at a rate of 4.5 °C per minute until it reached a temperature of 20-25 °C. Almost 500 grams of a liquid suspension was obtained, having about 45% solids. The suspension was kinetically stable for at least 2 months under normal pressure and temperature conditions.

Example 4: Detailed preparation of an emulsion or suspension according to the invention via the direct O/W method: S11 (see TABLE 1)

[0205] 350 grams of hydrogenated palm wax, having an iodine value < 10 grams of I2/IOO grams and 50 grams of soybean oil were mixed, introduced into an oil phase reactor and heated to about 95 ° C. 556 grams of water were introduced into an aqueous phase reactor, 20 grams of diethanolamine were added and the mixture heated to about 95 ° C. The oil phase was slowly added to the aqueous phase at a rate of 40 grams/min. The mixture was mixed at a stirring rate of 800 rpm. 10 grams of Tergitol® 15-S-9 were added. Subsequently, the mixture was cooled at a rate of 7°C per minute until it reached a temperature of 20-25°C. Almost 1000 grams of a liquid suspension were obtained, having about 48% solids. The suspension was kinetically stable for at least 1 month under normal pressure and temperature conditions.

Example 5: industrial scale-up of the preparation of a suspension according to the invention by the direct O/W method: S21 (see TABLE 1)

[0206] In a 4 m3 reactor, being equipped with a dispersant at 120 rpm, 1405 kg of water were introduced. 30 kg of diethanolamine and subsequently 35 kg of long chain fatty acid were loaded. 100 kg of soybean oil was loaded, along with 0.5 kg of anti-foaming agent. Subsequently, 25 kg of Tergitol 15-S-9 was added into the reactor. Then, 900 kg of solid powder of hydrogenated palm wax, having an iodine value < 10 grams of I2/100 grams, was added, at a rate of 50 kg/min, as well as another 2 kg of defoaming agent. The mixture is stirred at 120 rpm for 30 minutes at a temperature of 75 °C. While the mixture was cooled at a rate of 1°C per minute until it reached a temperature of 20-25°C, 2.5 kg of biocide was added. Almost 2500 kg of a liquid suspension was obtained, having about 48% solids. The suspension was kinetically stable for at least 4 months under normal pressure and temperature conditions. Variables such as Sauter diameter were comparable with the suspension obtained on a laboratory scale.

Example 6: Detailed preparation of an emulsion or suspension according to the invention via the EPI phase inversion method: S13 (see TABLE 1)

[0207] 175 grams of molten hydrogenated palm wax, having an iodine value < 10 grams of I2/IOO grams, 25 grams of soybean oil and 7 grams of long chain fatty acid were mixed, introduced into a phase reactor of oil and heated to around 70 °C, while stirring at around 150 rpm. 275 grams of water were introduced into an aqueous phase reactor, 10 grams of diethanolamine were added to obtain the anionic surfactant in situ through reaction with fatty acids, and the mixture was heated to about 70 °C. The oil phase was added to the aqueous phase at a rate of 30 grams/min and dispersed at a rate of 800 rpm. Subsequently, 5 g of Tergitol 15-S-9 are added and the mixture stirred at 800 rpm for 25 minutes. The mixture was cooled at a rate of 7 °C per minute until it reached 2025 °C. The suspension obtained was kinetically stable for at least 4 months, under normal pressure and temperature conditions.

Example 7: Detailed preparation of an emulsion or suspension by the combined EIP and PIT method: S2 (see TABLE 1)

[0208] 100 grams of BE-30 paraffin, 100 grams of molten hydrogenated palm wax, having an iodine value < 10 grams of I2/100 grams, and 7 grams of long-chain fatty acid were mixed in a phase reactor of oil and heated to approximately 80 °C by gently stirring at approximately 120 rpm. 275 grams of water were introduced into an aqueous phase reactor, 10 grams of diethanolamine were added to obtain in situ anionic surfactant, and the mixture heated to about 70 °C. The aqueous phase was added to the oil phase at a rate of 40 grams/min, with an ultraturrax rate of 10,000 rpm (EIP method). Once the addition is complete, 10 grams of Findet 1618-AR surfactant was added, maintaining a temperature of at least 85 °C (PIT method). The mixing was maintained for 20 min. The mixture was homogenized at 35 MPa (350 bar). The mixture was then cooled to 20-25°C at a rate of 6°C per minute to obtain an O/W suspension. The suspension obtained was stable for at least 1 month.

Example 8: Comparative z-potential of commercial FORESA WAX 2102 paraffin suspension and S21 suspension of the invention

[0209] Zeta Potential analysis is a technique for determining the surface charge of nanoparticles in solution (colloids). Zeta Potential is an indicator of electrostatic interactions between particles and is typically used to predict the colloidal stability of a dispersion. The Zeta Potential was obtained from the electrophoretic mobility by applying the Smoluchowski approximation or thin double layer assumption. TABLE 2 shows the results corresponding to the z-potential obtained for the two samples under study: S21 of the invention and a commercial paraffin suspension, marketed as FORESA WAX 2102, which has a solids content between 58 and 62% and a shelf life at 20 °C for 6 months.

[0210] Both samples showed negative z-potential values. Sample S21 has a more negative z-potential than sample FORESA WAX 2102, which indicates superior colloidal stability of S21.

Example 9: Scanning electron microscopy (SEM) images of the commercial FORESA WAX 2102 paraffin suspension and the S21 suspension of the invention

[0211] SEM is a technique for examining and analyzing the surface morphology of samples. The electron beam from an electron gun column is reduced by condenser lenses into a fine spot as small as 1 nm in diameter that is swept across a selected area of the sample surface. The interactions between the electron beam and the overall sample differ in intensity signals that are collected by detectors and stored in computer memory to be subsequently mapped as variations in brightness on the image display. The most widely used signal produced by interactions of the primary electron beam with the sample is the secondary electron emission signal which varies with the topography of the sample surface being dark for the recesses and bright for the edges. Image magnification is determined by the ratio of the size of the displayed image to the size of the scanned area on the sample.

[0212] Figures 1 a) and b) show representative SEM images corresponding to the FORESA WAX 2102 sample. As can be seen, the sample is homogeneously distributed on the surface of the glass slide on which it was deposited, starting the formation of a film ( Figure a)). In some parts of the sample, it is possible to observe some spherical morphology that could be due to the formation of particles before their coalescence as a film (Figure b)).

[0213] Figures 2 a) and b) show representative SEM images corresponding to sample S21 of Example 5. As can be seen, the sample consists of well-separated spheres that exhibit high polydispersity.

Example 10: Preparation of a formulation of the invention comprising urea as a formaldehyde scavenger

[0214] 100 g of BE-30 paraffin, 100 g of hydrogenated palm wax, having an iodine value of less than 10, are charged, and 10 grams of a fatty alcohol ethoxylate of HLB (lipophilic-hydrophilic balance) between 10 and 14 are added to the oil phase in the oil phase reactor. This mixture is kept under stirring and at a minimum temperature of 60 °C, between 60 °C and 95 °C, preferably between 70 °C and 80 °C. 10 g of long-chain fatty acid is incorporated into the oil phase reactor.

[0215] 600 g of water is introduced into the aqueous phase reactor, it is maintained under stirring and at a temperature of at least 60 °C and a maximum of 100 °C, preferably between 70 °C and 80 °C. Subsequently, the corresponding ethanolamine for soap formation is then incorporated, for example, 7 g of diethanolamine. The formaldehyde sequestrant and/or catalyst are then slowly incorporated, for example 200 g of urea are incorporated.

[0216] The oil phase is slowly added to the aqueous phase and the mixture is kept under stirring at a preferred temperature of 75 °C.

[0217] The pre-emulsion is homogenized in a homogenizer, the homogenizer pressure is set between 0 and 350 kg/cm2 hydraulic, depending on the desired final particle diameter, and then cooled to 25 °C.

[0218] For the same emulsification conditions provided, the particle diameter is inversely proportional to the applied pressure; If desired, the suspensions can be recirculated before cooling, passing them 2 or more times through the homogenizer to further reduce the particle diameter.

[0219] The same procedure can be used to add a catalyst for formaldehyde-derived resins, or both a formaldehyde scavenger and a catalyst for formaldehyde-derived resins.

Example 11: Preparation of a formulation of the invention, comprising urea as a formaldehyde scavenger and ammonium bisulfite as a catalyst for formaldehyde-derived resins

[0220] A suspension of hydrogenated palm oil with a solids content of 40% according to the invention is prepared, at room temperature, and separately, an aqueous solution of the formaldehyde sequestrant and/or the catalyst are prepared: a solution of urea, which has a solids content of 50% and 70% ammonium bisulfite.

[0221] 250 g of a 50% urea solution and 500 g of a wax suspension of the invention, having a solids content of 40% are mixed under normal temperature conditions and under stirring in a reactor. Once the entire urea solution is dissolved, 250 g of 70% ammonium bisulfite is added very slowly to the above mixture under normal temperature conditions and under stirring.

[0222] At the end of the process, a formulation having a solids content of 50%, which comprises waxes or vegetable oils to satisfy the hydrophobic function of the formulation, urea as a formaldehyde sequestrant and ammonium bisulfite as a catalyst for the aminoplastic resin .

Example 12: Water resistance of MDF boards manufactured using the formulations of the invention versus using commercial state-of-the-art paraffin suspension

[0223] The industrial MDF board (medium density fiberboard) was manufactured with the industrial scale suspension of the S21 suspension, as obtained in Example 5.

[0224] It was possible to manufacture the MDF with absolute normality for more than three hours of industrial production, isolating around 50 m3 correctly identified manufactured with the S21 suspension; The MDF was cut in line to a size of 4940 x 2500 x 2.5 mm; it was a board intended for the manufacture of fruit boxes.

[0225] In TABLE 3 below, working conditions and quality results are presented comparing the suspension of vegetable waxes against a state-of-the-art paraffin wax suspension, FORESA WAX 2102, available from the Spanish company FORESA, SA ( see Introduction to Examples for details).

Example no. 13. Manufacturing of MDF boards in a pilot-scale industrial plant; Comparison of waterproofing capacity, formaldehyde emission and hardening with the use of formulations according to the invention versus prior art commercial paraffin emulsions

[0226] MDF boards were manufactured to show the effectiveness of the formulations according to the present invention in comparison with prior art boards, obtained with the use of paraffin-based emulsions instead of the formulations according to the invention ; its hydrophobic capacity, its catalytic capacity for formaldehyde-based resins and its properties to sequester formaldehyde were tested, in comparison with prior art plates.

[0227] For this purpose, the formulations obtained according to examples 10 and 11 of the present invention were used in the manufacture of the plates.

[0228] To compare the properties of the plates obtained, the plates were manufactured using a commercial paraffin suspension, FORESA WAX 1102 (see introductory part of the Examples for further details), with the addition of a formaldehyde sequestrant and/or a catalyst to cure formaldehyde.

[0229] The main working conditions for manufacturing the plates in a plate press with dimensions of 500 mm x 500 mm were as follows: - Chipboard quality: E1 according to EN 120. - Thickness: 16 mm - Suspension of wax: FORESA WAX 1102 (paraffin-based) versus formulations (vegetable oil-based) formulations of examples 10 and 11, according to the invention. - Press factor: 9.0 s/mm. - Temperature of press plates: 200 °C - Gluing rate: 10% by weight (dry resin/dry wood). - SO4(NH4)2 stiffener: 0 to 2.0% by weight (dry stiffener/dry wood). - Resin used: urea-formaldehyde resin (UF), without melamine and the molar ratio of formaldehyde/NH2 in the range of 0.5 to 0.55; available to the public from the Spanish company FORESA, S.A., offered under the name FORESA RES 1350. - Urea as formaldehyde sequestrant: 0 to 2% by weight (amount of dry urea in relation to dry wood).

[0230] In view of the results presented in TABLE 4, it can be concluded that:

[0231] The results confirm that the formulations according to the invention of examples 10 and 11 simultaneously manage to improve the hydrophobicity of the plates, catalyze the hardening of the formaldehyde-based resins used in the manufacture of said plates, and sequester free formaldehyde in said plates. wood-based boards. The use of the formulations in examples 10 and 11 results in obtaining agglomerates with a very low formaldehyde content and emission, in addition to improving the final hydrophobic properties of the boards, compared to a commercial paraffin-based resin.

[0232] Comparing the results obtained from the plates identified with numbers 1,2,3 and 4 in TABLE 4 (manufactured using a commercial paraffin-based formulation), the data regarding swelling, free formaldehyde content and formaldehyde emission are much worse than the data for the plates obtained within the formulations of the present invention, identified in TABLE 4 with numbers 5, 6, 7 and 8.

Example no. 14. Manufacture of particle boards in an industrial plant; Comparison between formulations according to the invention versus commercial prior art paraffin emulsion

[0233] To verify the industrial scalability of the invention, an industrial test was performed, manufacturing, at a rate of 60 m3/hour, in a continuous industrial press.

[0234] The agglomerated plates were manufactured to show the effectiveness of the formulations according to the present invention in comparison with the prior art plates, obtained with the use of commercial paraffin-based emulsions instead of the formulations according to the invention ; its hydrophobic capacity, its catalytic capacity for formaldehyde-based resins and its properties to sequester formaldehyde were tested, in comparison with prior art plates.

[0235] For this purpose, the formulations obtained according to examples 10 and 11 of the present invention were used in the manufacture of the plates.

[0236] To compare the properties of the plates obtained, the plates were manufactured using a commercial paraffin suspension, FORESA WAX 1102 (see introductory part of the Examples for further details), with the addition of a formaldehyde sequestrant and/or a catalyst to cure formaldehyde.

[0237] The main working conditions for manufacturing the particle board were as follows: - Chipboard quality: E1 according to EN 120 and CARB 2 according to ASTM-13333. - Thickness: 16 mm - Wax suspension: FORESA WAX 1102 (paraffin-based) versus formulations (vegetable oil-based) formulations of examples 10 and 11, according to the invention. - Press factor: 4.5 s/mm. - Temperature of press plates: 240 °C - Core layer gluing rate: 8% by weight (dry resin/dry wood). - Bonding rate surface layer: 10% by weight (dry resin/dry wood). - SO4(NH4)2 stiffener: 0 to 2.0% by weight (dry stiffener/dry wood). - Resin used: melamine-urea-formaldehyde resin, a urea-formaldehyde resin containing melamine in the range of 2 to 5% by weight and a formaldehyde/NH2 molar ratio in the range of 0.5 to 0.55; available to the public from the Spanish company FORESA, S.A., offered under the name FORESA RES 2120. - Urea as formaldehyde sequestrant: 0 to 2% by weight (dry urea/dry wood).

[0238] The physicochemical properties of the plates manufactured using the formulations of examples 10 and 11 according to the present invention show the following:

[0239] The lowest values in terms of formaldehyde content and formaldehyde emission are obtained when example formulations 10 and 11 are used, see the data for the plates identified as 3,4,5,6 and 7 in TABLE 5 .

[0240] These results confirm that the formulations according to the invention of examples 10 and 11 according to the invention, provide agglomerated boards with very low formaldehyde content and formaldehyde emission: formaldehyde below 3.0 mg per 100 g of dry board according to the European standard EN 120, and with values close to 1 mg of formaldehyde per m2 and hour in the case of the formaldehyde emission test according to the European standard EN 717-2.

Example No. 15. Comparison of waterproofing capacity of suspensions having iodine indices below 10 (state of the art) versus above 10 (according to the invention)

[0241] MDF boards were manufactured to test the hydrophobic effectiveness of the formulation of Example No. 5 of the invention, in comparison with MDF boards manufactured under the same conditions using a commercial vegetable oil emulsion, available through the reference AGRI PURE™ AP- 635 from Cargill (https://www.cargill.com/bioindustrial/agri-pure-vegetable- waxes), having an iodine value below 10.

[0242] The main working conditions for manufacturing the chipboard in a board press with dimensions of 500 mm x 500 mm were as follows: - Chipboard quality: E1 according to EN 120. - Thickness: 16 mm - Suspension of wax: AGRIPURE AP-635 formulation versus the formulation according to EXAMPLE 5 of the invention. - Press factor: 9.0 s/mm. - Temperature of press plates: 200 °C - Gluing rate: 10% by weight (dry resin/dry wood). - SO4(NH4)2 stiffener: 0.4% by weight (dry stiffener/dry wood). - Resin used: Urea-formaldehyde without melamine, and a molar ratio of formaldehyde/NH2 in the range of 0.5 to 0.55; available to the public from the Spanish company FORESA, S.A., offered under the name FORESA RES 1350.

[0243] In view of the results shown in TABLE 6, it can be concluded that:

[0244] The waterproofing capacity of a formulation according to the invention, having an iodine value above 10, i.e. which is kinetically stable (without unemulsified waxes) is much better than the use of hydrogenated oil emulsions vegetable having an iodine index less than 10.

[0245] It appears that the soybean oil content can help stabilize the suspension of vegetable waxes and, therefore, increase the waterproofing capacity of the formulation as it improves distribution in the hydrophilic fibers to which this O/W suspension is applied.

Example 16: Comparison of waterproofing capacity of MDF boards manufactured using a formulation according to the invention versus prior art commercial synthetic wax emulsions/state of the art commercial paraffin emulsions

[0246] MDF boards were manufactured to test the hydrophobic effectiveness of the formulation of Example No. 5 of the invention, in comparison with MDF boards manufactured under the same conditions using a prior art commercial synthetic wax emulsion (HYDROWAX ® PRO A 18, a liquid synthetic wax blend emulsion, available from SASOL: https://cdn.sasoldigital.com/stagingpic/products/home/grade s/EU/5hydrowax-pro-a18/index.html) and a state-of-the-art commercial paraffin emulsion (FORESA WAX 2102, available from the Spanish Company FORESA, S.A.; see the introductory part of the Examples for additional details).

[0247] The main working conditions for manufacturing the chipboard in a board press with dimensions of 500 mm x 500 mm were as follows: - Chipboard quality: E1 according to EN 120. - Thickness: 16 mm - Suspension of wax: formulation according to the EXAMPLE - of the invention versus HYDROWAX® PRO A 18 versus FORESA WAX 2102 - Press factor: 9.0 s/mm. - Temperature of press plates: 200 °C - Gluing rate: 10% by weight (dry resin/dry wood). - SO4(NH4)2 stiffener: 0.4% by weight (dry stiffener/dry wood). - Resin used: Urea-formaldehyde without melamine, and a molar ratio of formaldehyde/NH2 in the range of 0.5 to 0.55; available to the public from the Spanish company FORESA, S.A., offered under the name FORESA RES 1350.

[0248] In view of the results shown in TABLE 7, it can be concluded that:

[0249] The waterproofing capacity of a formulation according to the invention, based on vegetable oil, is similar or even slightly better than the waterproofing capacity achieved with the prior art paraffin emulsion (FORESA WAX 2102) or state-of-the-art synthetic wax blend emulsion (HYDROWAX® PRO A 18) (see e.g. data for swelling according to EN317 and water absorption).

Example 17. Study of the kinetic stability of formulation S21 according to the invention, obtained in Example 5, by monitoring its rheological profile for one year.

[0250] The formulation S21 according to the invention, obtained in Example 5, which has an iodine value above 10 for the total amount of oil, was sent for a rheological study over the course of one year.

[0251] Samples were taken on different dates (namely, 03/28/2017, 04/18/2017, 05/09/2017, 08/28/2017 and 03/27/2018) and each was sent to a measurement of the viscosity at different shear rates and the Sauter diameter of the emulsion oil particles. The data obtained is shown in TABLE 8:

[0252] The viscosity measured at different shear rates for each sample is also shown in the graph in Fig. 3 (the different dates are reflected by different formats).

[0253] As can be seen, the Sauter diameter is extremely stable over time, which is a sign of kinetic stability, that is, that neither phase separation occurs nor any solid particles are formed during the time of the tests. .

[0254] In the case of viscosity, although for an intermediate sample the viscosity increased, the values returned to normal values at a later stage.

[0255] These results show that the formulation according to invention S21 is kinetically stable.

Example 18. Study of the kinetic stability of formulation S8 (comparative example)

[0256] Formulation S8 (see TABLE 1 for details) which has an iodine value below 10 for the total amount of oil, was sent for Sauter diameter measurements 4 weeks.

[0257] TABLE 9 reflects the average Sauter Diameter measured in week 0 (freshly prepared formulation) and weeks 1, 2, 3 and 4.

[0258] The graph in Fig. 4 reflects the distribution of the Sauter diameter of the particles, at the same points in time (i.e., weeks 0, 1, 2, 3 and 4), for formulation S8.

Claims (23)

1. Vegetable oil-based formulation characterized by being kinetically stable; wherein it comprises an oil-in-water (O/W) suspension, which comprises: - from 1% by weight to 5% by weight of surfactant, wherein the surfactant is at least one anionic surfactant and at least one nonionic surfactant ; the surfactant being added as such or obtained in situ by adding between 1 and 3% by weight of an ethanolamine; - 15% by weight to 50% by weight of hydrogenated or partially hydrogenated palm oil; - from 0 to 25% by weight of paraffin; - from 2 to 8% by weight of soybean oil; and wherein - the total amount of oils, being the sum of palm oil, paraffin and soybean oil in the O/W suspension does not exceed 55% by weight; - within the total amount of oils, 2 to 10% by weight is non-hydrogenated oil, and the rest is hydrogenated and/or partially hydrogenated oil; - the iodine value of the total quantity of oils is at least 10 g of iodine per 100 g of total quantity of oils; - the O/W suspension has a solids content of between 30% by weight and 55% by weight, and the rest of the suspension, until it reaches 100% by weight, is water, the solids content comprising all components that are different of water. 2. Vegetable oil-based formulation according to claim 1, characterized in that it comprises up to 25% by weight of a formaldehyde sequestrant, in relation to the total weight of the formulation. 3. Vegetable oil-based formulation according to any one of claims 1 or 2, characterized in that it comprises up to 25% by weight of a catalyst for curing formaldehyde-derived resins, in relation to the total weight of the formulation. 4. Vegetable oil-based formulation according to any one of claims 1 to 3, characterized in that the soybean oil is non-hydrogenated soybean oil having an iodine value between 120 and 155 g of iodine per 100 g of soybean oil. 5. Vegetable oil-based formulation according to any one of claims 1 to 4, characterized in that the solids content is between 45% by weight and 55% by weight. 6. Vegetable oil-based formulation according to any one of claims 1 to 5, characterized in that the O/W suspension contains up to 25% by weight of paraffin. 7. Vegetable oil-based formulation according to any one of claims 1 to 6, characterized in that the O/W suspension contains between 4 and 8% by weight of soybean oil. 8. Formulation according to claim 6, characterized in that the paraffin is semi-refined paraffin. 9. Formulation according to any one of claims 1 to 8, characterized in that at least 50% by weight of the fatty acids in the total amount of oils are fatty acids having 20 to 22 carbon atoms. 10. Formulation according to any one of claims 1 to 9, characterized in that the non-ionic surfactant is selected from secondary alcohol ethoxylate and ethoxylated fatty alcohol. 11. Formulation according to any one of claims 1 to 10, characterized by the fact that the T/O ratio, that is, the ratio of surfactant/total amount of oil in the O/W suspension, is between 4% and 15%. 12. Formulation according to any one of claims 2 to 11, characterized in that the formaldehyde sequestrant is at least one selected from urea, monoethanolamine and diethanolamine. 13. Formulation according to any one of claims 3 to 12, characterized in that the catalyst for curing resins is at least one selected from ammonium bisulfite, ammonium nitrate and ammonium sulfate. 14. Method for obtaining an O/W suspension, as defined in any one of claims 1 to 13, characterized in that it comprises: - adding a water phase to an oil phase, at least one of which contains an anionic surfactant or non-ionic, in such an amount to obtain a concentration of between about 1 wt % and about 5 wt % in the final emulsion, thus obtaining a W/O emulsion, until the W/O emulsion is inverted to an O emulsion /A; - heat the O/W emulsion to at least 75 °C, to obtain a W/O emulsion; - cooling the W/O emulsion to room temperature, to obtain the O/W suspension, as defined in any one of claims 1 to 9. 15. Use of a formulation as defined in any one of claims 1 to 13, characterized in that it is in the manufacture of articles selected from wood-derived boards, wood composite boards, fiber boards, agglomerates, compacted boards, plywood, cardboard, oriented particle board, stone wool or fiberglass insulation, or combinations thereof. 16. Use according to claim 15, characterized by the fact that the articles are manufactured by using a formaldehyde-based resin. 17. Use according to any one of claims 15 or 16, characterized in that it is to increase the hydrophobicity of the manufactured articles. 18. Use, according to claim 16, of the formulation, as defined in any one of claims 2 to 12, characterized in that it is to reduce free formaldehyde in manufactured articles. 19. Use, according to claim 18, characterized in that it is to reduce the emission of formaldehyde from wood-based boards, wood composite boards, fiber boards, agglomerates, compacted boards, plywood, cardboards, oriented particle boards, insulation of fiberglass or stone wool insulation, to 1 mg of formaldehyde per square meter and hour, or below, as measured by the gas analysis method UNE-EN ISO 12460-3:2016. 20. Use, according to any one of claims 15 to 19, of the formulation, as defined in any one of claims 3 to 12, characterized in that it is to catalyze the hardening of the formaldehyde-based resin. 21. Use, according to any one of claims 15 to 20, characterized in that it is to improve the release of manufactured articles from their molds. 22. Plates characterized by comprising a formulation, as defined in any one of claims 2 to 13, which has a formaldehyde emission of 1 mg of formaldehyde per square meter and hour, or below, as measured by the UNE-EN gas analysis method ISO 12460-3:2016. 23. Stone wool or fiberglass insulation comprising a formulation as defined in any one of claims 2 to 13 that has a formaldehyde emission of 1 mg of formaldehyde per square meter and hour, or below, as measured by the UNE-EN ISO 12460-3:2016 gas analysis method.