WO2019180236A1 - Hydrophobing and formaldehyde scavenging compositions comprising wax emulsions and resorcinol and their use for increasing the hydrophobicity of wood composite boards and fibreglass or rock wool insulations - Google Patents
Hydrophobing and formaldehyde scavenging compositions comprising wax emulsions and resorcinol and their use for increasing the hydrophobicity of wood composite boards and fibreglass or rock wool insulations Download PDFInfo
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- WO2019180236A1 WO2019180236A1 PCT/EP2019/057304 EP2019057304W WO2019180236A1 WO 2019180236 A1 WO2019180236 A1 WO 2019180236A1 EP 2019057304 W EP2019057304 W EP 2019057304W WO 2019180236 A1 WO2019180236 A1 WO 2019180236A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission
Definitions
- the present invention relates to compositions comprising O/W wax emulsions, including petroleum derived and vegetable derived wax emulsions, and resorcinol.
- the compositions according to the invention are useful for preparing hidrofugant formulations, i.e. waterproofing formulations; they may be used in the manufacture of several materials, for example of wood composite boards, such as wood derived boards, fibreboards, particleboards, chip boards, oriented strand boards, plywood and paperboards, but also of fibreglass or rock wool insulations.
- the formulations according to the invention are also useful for favouring the release of the materials manufactured therewith from molds and machinery used during manufacture, for reducing the formaldehyde emission, if formaldehyde is used during the manufacture of the materials, and allowing for lower press temperature and press factor during the manufacture of boards.
- the manufacture of wood composite boards such as particleboard, fibreboard (MDF and HDF), chip boards, oriented strand boards and the like generally first comprises combining wood chips, fibres or particles and an adhesive. The mixture is then heated under pressure to cure the adhesive and to form the desired board.
- Formaldehyde based resins such as phenol-formaldehyde (PF) are typical adhesives used in the manufacture of such panels.
- Manufacture of fiberglass insulations and rock wool insulations generally comprises a step of manufacture of the rock wool and fiberglass themselves, which can be performed by different procedures, for example according to the techniques known in the state of the art as rotary process (internal centrifuge), cascade process (external centrifuge), and flame attenuation process (pot & marble).
- an adhesive resin generally a thermosetting resin
- the mixture of fibers and resin is subjected to a thermal treatment, at a temperature generally higher than 100 °C, in order to effect the polycondensation of the resin and thus obtain a thermal and/or acoustic insulation product.
- Commonly used adhesive compositions are resins derived from formaldehyde, similar to those used in the manufacture of wood derived boards or wood composite boards. During the manufacture further additives may be added to the mixture of fibers and adhesive, such as for example catalysts for crosslinking the resin or waterproofing emulsions (typically paraffin-based).
- Formaldehyde is a monomer, which is used to polymerize with urea, melamine, phenol to form aminoplast resins.
- Formaldehyde is under discussion as an indoor air pollutant since the 1960s(O. Wittmann (1962), Holz Roh- Werkst, 20, 221 - 224), when the release of formaldehyde from particleboard during use was documented.
- Formaldehyde emissions from materials bonded with urea formaldehyde resin were soon identified as the cause of the complaints.
- REACH Registration, Evaluation, Authorization and Restriction of Chemicals
- It is the main framework for chemical regulation in the European Union and adopted to improve the protection of human health and the environment from the risks that can be posed by chemicals.
- REACH not only applies to those chemicals used in industrial processes but also to chemicals in products for intended use at the customers site, for example building materials, textiles, consumer products and other appliances.
- CSR Chemical Safety Report
- the definition of a Group 1 carcinogen according to IARC is as follows:“There is enough evidence to conclude that it can cause cancer in humans”.
- the evaluation is based on information regarding the relationship between nasopharyngeal cancer and leukaemia related to the exposure to formaldehyde (International Agency for Research on Cancer (IARC), 2006).
- Category 1 B states that the carcinogenic effect has been demonstrated in animal trials and is probable for humans. The reclassification results in a series of consequences depending on national legislation.
- SCOEL Scientific Committee on Occupational Exposure Limits
- TWA time-weighted average
- STEL Short Term Exposure Limit
- SCOEL Scientific Committee on Occupational Exposure Limits
- the formaldehyde WHO guideline value is also considered defendable for prevention of all types of cancer, including lymphohema- topoietic malignancies.
- the Committee on Indoor Guide Values has outlined the following:“Based on a NOAEC (no observed adverse effect concentration) of 0,63 mg/m 3 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...
- RW I indoor air guide value
- the indoor air guide value for formaldehyde is also protective against cancer risk of inhaled formaldehyde” ( Ausschuss fUr iensraumrichtagonist, 2016a).
- the same committee stated that on the basis of the current data there is no clear association between formaldehyde exposure in the indoor environment and asthma in children (Ausschuss fUr iensraumrichtagonist, 2016b).
- UNE-EN ISO 12460-3:2016 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).
- ASTM D5582-00 (Reapproved 2006), Standard Test Method for Determining Formaldehyde Levels from Wood Products Using a Desiccator.
- This test method describes a small-scale procedure for measuring formaldehyde emissions potential from wood products.
- the formaldehyde level is determined by collecting airborne formaldehyde in a small distilled water reservoir within a closed desiccator.
- the quantity of formaldehyde is determined by a chromotropic acid test procedure.
- ASTM D6007-02 Standard Test Method for Determining Formaldehyde Concentrations in Air from Wood Products Using a Small-Scale Chamber.
- This test method measures the formaldehyde concentrations in air from wood products under defined test conditions of temperature and relative humidity. Results obtained from this small-scale chamber test method are intended to be comparable to results obtained testing larger product samples by the large chamber test method for wood products, Test Method E 1333.
- ASTM E1333-10 Standard Test Method for Determining Formaldehyde Concentrations in Air and Emission Rates from Wood Products Using a Large Chamber.
- This test method measures the formaldehyde concentration in air and emission rate from wood products containing formaldehyde under conditions designed to simulate product use. The concentration in air and emission rate is determined in a large chamber under specific test conditions of temperature and relative humidity. The general procedures are also intended for testing product combinations at product-loading ratios and at air- exchange rates typical of the indoor environment.
- Document WO 2010/054467 A1 describes emulsions having a high wax content, comprising formaldehyde scavengers; the formaldehyde scavengers are preferably selected from urea, a urea derivative, a urea resin, a urea-formaldehyde resin, a melamine- urea-formaldehyde resin, an ethylene urea compound, carbohydrazide, a natural polyphenol, tannin, lignin, lignosulphonate, or a combination thereof.
- formaldehyde scavengers are preferably selected from urea, a urea derivative, a urea resin, a urea-formaldehyde resin, a melamine- urea-formaldehyde resin, an ethylene urea compound, carbohydrazide, a natural polyphenol, tannin, lignin, lignosulphonate, or a combination thereof.
- urea a urea derivative, a urea resin, a urea-formaldehyde resin, a melamine- urea-formaldehyde resin, an ethylene urea compound, carbohydrazide, a natural polyphenol , tannin, lignin, lignosulphonate, or a combination thereof.
- scavengers for example natural or bio-based scavengers ( Eom Y-G et al. (2006), Mokchae Konghak 34:29-41; Kim S et al. (2009); Constr Build Mater 23(6), 2319-2323; Kim S et al. (2006), Macromol Mater Eng 291(9), 1027-1034) or other compounds having 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), in order to reduce formaldehyde emission from wood-based boards, is commonly adopted.
- natural or bio-based scavengers Eom Y-G et al. (2006), Mokchae Konghak 34:29-41; Kim S et al. (2009);
- the molar ratio of the resins used is too low: 0,90 moles of formaldehyde per mole of urea.
- the tensile mechanical properties are very low for the industrial quality standards accepted by the EPF (European Panel Federation).
- Resorcinol also called m-dihydroxybenzene or 1 ,3-dihydroxybenzene
- Resorcinol is a phenolic compound used in the manufacture of resins, plastics, dyes, medicine, and numerous other organic chemical compounds. It is produced in large quantities by sulfonating benzene with fuming sulfuric acid and fusing the resulting benzenedisulfonic acid with caustic soda. Reaction with formaldehyde produces resins used to make rayon and nylon amenable to impregnation with rubber, and as adhesives. As a chemical intermediate, resorcinol is converted to dyes, explosives, and pharmaceuticals; it is also employed in photographic developers and cosmetics. In medicine it is used externally in ointments and lotions as an antifungal.
- phenolic resins can be made with significant decreases in cure time compared with PF resin adhesives.
- the chemistry associated with the formation and curing of phenol-resorcinol-formaldehyde (PRF) and resorcinol-formaldehyde (RF) resins, is similar to that for PF resins.
- PRF and RF prepolymers are made at a low formaldehyde molar ratio and thus are essentially novolac resins.
- the prepolymers which are stable, are cured by the addition of a hardener (e.g., paraformaldehyde or a formaldehyde solution).
- a hardener e.g., paraformaldehyde or a formaldehyde solution.
- the PRF and RF resin adhesives are used in situations where fast or room temperature curing is required (e.g., finger jointed structures) or where the wooden assembly that is being bonded is too thick to allow that sufficient heat is transferred to the inside of said assembly (e.g., laminated timbers), so that the resin is cured at the bond lines.
- the main disadvantage of these resins is the much higher cost of resorcinol compared with that of phenol.
- Resorcinol has been used in the production of rubber coated fabrics, particularly for increasing the adhesiveness of the fabrics with respect to rubber.
- GB1259470 discloses an emulsion comprising paraffin hydrocarbons and resorcinol as monomers and/or precondensates of thermosetting plastics, among other components.
- GB2136008 discloses a formaldehyde binder composition, which comprises at least one organic hydroxy compound and at least one amide, in water. Glycerine as the organic hydroxy compound and urea as the amide compound are shown in the Examples to present a synergistic behaviour. Resorcinol as a further organic hydroxy compound is compared to monoethyleneglycol, dextrin and phenol, the composition comprising resorcinol showing the smallest reduction in formaldehyde.
- the present invention provides hydrophobing and formaldehyde scavenging compositions, comprising and O/W suspension or emulsion, comprising at least one petroleum derived or at least one vegetable derived wax or oil, or a mixture thereof, and resorcinol, the compositions being useful for increasing the hydrophobicity of wood composite boards (including wood derived boards, fibreboards, particleboards, chip boards, oriented strand boards, plywood and paperboards), as well as of fibreglass or rock wool insulations, when used during their manufacture.
- wood composite boards including wood derived boards, fibreboards, particleboards, chip boards, oriented strand boards, plywood and paperboards
- fibreglass or rock wool insulations when used during their manufacture.
- compositions of the invention allows to obtain boards or insulations not only having good hydrofugant properties, but also having a formaldehyde emission of 0,005 mg of formaldehyde per square meter and hour or below, as measured by gas analysis method UNE-EN ISO 12460-3:2016.
- a first object of the invention is a hydrophobing and formaldehyde scavenging composition, which comprises:
- an O/W suspension or emulsion which as the non-aqueous phase comprises at least one petroleum derived or at least one vegetable derived wax or oil, or a mixture of at least one petroleum derived and at least one vegetable derived wax or oil;
- the weight ratio of wax or oil with regard to resorcinol in the composition is between 4:1 and 1 :4, the weight of wax or oil and resorcinol together being between 45 wt.% and 70 wt.% of the composition.
- a further object of the invention is the use of the composition of the invention for increasing the hydrophobicity of hydrophilic materials (such as wood composite boards (including wood derived boards, fibreboards, particleboards, chip boards, oriented strand boards, plywood and paperboards) as well as fibreglass or rock wool insulations).
- hydrophilic materials such as wood composite boards (including wood derived boards, fibreboards, particleboards, chip boards, oriented strand boards, plywood and paperboards) as well as fibreglass or rock wool insulations).
- wood composite boards and fibreglass or rock wool insulations comprising a formaldehyde derived resin or adhesive and the composition of the invention, having a formaldehyde emission of 0,005 mg of formaldehyde per square meter and hour, or below, as measured by gas analysis method UNE-EN ISO 12460- 3:2016.
- compositions of the invention comprise an O/W suspension or emulsion comprising at least one at least one petroleum derived or at least one vegetable derived wax or oil.
- An emulsion is a“fluid colloidal system in which liquid droplets and/or liquid crystals are dispersed in a liquid. The droplets often exceed the usual limits for colloids in size.
- An emulsion is denoted by the symbol O/W if the continuous phase is an aqueous solution and by W/O if the continuous phase is an organic liquid (an 'oil'). More complicated emulsions such as O/W/O (i.e. oil droplets contained within aqueous droplets dispersed in a continuous oil phase) are also possible.”
- a suspension according to the IUPAC, is“a liquid in which solid particles are dispersed”.
- paraffin suspensions are often named as paraffin emulsions, in fact they are suspensions, as the droplets of oil in the water phase, at normal temperature and pressure conditions, are in solid state. Therefore, the suspension and emulsion will be used indistinctively throughout the present description.
- the formulations as such are liquid in order to allow an easy application.
- Emulsifiers are a group of substances of different origin and properties that will contribute to a greater stabilization of the emulsions or suspensions; this is due mainly to its amphiphilic or double affinity character, which, from the physico-chemical point of view, is defined as a double polar and apolar property. Within this large group of compounds we can find e.g. surfactants.
- Formaldehyde scavenger in the frame of the present invention refers to any compound that allows to reduce the content of free formaldehyde in any product or composition. Any formaldehyde scavenger known in the State of the Art may be used.
- the formaldehyde scavenger may be selected from, but is not limited to, urea, urea derivatives, hexamine, amino group containing compounds, hexamine, sulphite salts and metabisulphite salts.
- Non-ionic surfactants are surfactants that do not bear an electrical charge.
- hydrophilic properties are conferred on them by the presence of a number of oxygen atoms in one part of the molecule which are capable of forming hydrogen bonds with molecules of water.
- many long chain alcohols exhibit some surfactant properties, such as fatty alcohols, cetyl alcohol, stearyl alcohol, and cetostearyl alcohol, and oleyl alcohol.
- Other non-ionic surfactants are alcohol ethoxylates, polyglycol ethers, polyoxyethylene alkyl ethers, secondary alcohol ethoxylates, polyoxyethylene alkyl ethers, polyalkyl glycol alkyl ethers (e.g. polyethylene and polypropylene glycol alkyl ethers), glucoside alkyl ethers, polyethylene glycol alkylphenyl ethers or glycerol alkyl esters.
- “Anionic surfactants” are surfactants that contain anionic functional groups at 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 laureth sulfate (sodium lauryl ether sulfate or SLES), and sodium myreth sulfate.
- docusate dioctyl sodium sulfosuccinate
- PFOS perfluorooctanesulfonate
- alkyl-aryl ether phosphates alkyl ether phosphates
- alkyl ether phosphates anionic surfactants.
- “Sauter mean diameter”, also designated as D(3,2), D32 or D(32) is the mean diameter with the same ratio of volume to surface area as the entire ensemble It was originally developed by German scientist Josef Sauter in the late 1920s.
- the size of drops is determined based on the absorption/scattering of light. The technique depends on the fact that absorption/scattering is proportional to the surface area of the drops.
- Normal temperature and pressure conditions refers to a temperature of 20 °C and an absolute pressure of 1 atm.
- O/W emulsion refers to an oil in water emulsion.
- O/W suspension refers to a suspension comprising solid particles of hydrogenated oil (wax) suspended in water; the terms suspension and emulsion are used indistinctively along the present description.
- Formaldehyde based resins or“formaldehyde derived resins”, as used in the frame of the present invention, refers to any resin or plastic which is produced from formaldehyde with other reactants, such as urea, phenol, or melamine.
- urea- formaldehyde resin is a non-transparent thermosetting resin or plastic, produced from urea and formaldehyde. They are used in adhesives, finishes, particleboard, MDF, and molded objects.
- Phenol formaldehyde resins (PF) or phenolic resins are synthetic polymers obtained by the reaction of phenol or substituted phenol with formaldehyde.
- Melamine formaldehyde resin is a hard, thermosetting plastic material made from melamine and formaldehyde by polymerization. In its butylated form, it is dissolved in n-butanol and xylene. It is then used to cross-link with alkyd, epoxy, acrylic, and polyester resins, used in surface coatings. There are many types, varying from very slow to very fast curing.
- Wood composite boards in the frame of the present invention refers to boards obtained by binding and compressing natural fibres, optionally in combination with synthetic fibres, Examples thereof, but not limited to, are particleboard, fibreboard (MDF and HDF), chip boards, oriented strand boards and plywood.
- Synthetic fibres in the frame of the present invention refers to fibres from polyester, polyethylene or polypropylene.
- Natural fibres in the frame of the present invention refers to wood fibres, chips, particles, flakes or strands, and/or other natural fibres like flax, hemp, rye straw, wheat straw, rice straw, hemp stalks, kenaf stalks or sugar cane residues.
- Catalyst for curing formaldehyde based resins in the frame of the present invention, is meant to be any substance suitable to be used to cure formaldehyde based resins. It may be selected from the group comprising ammonium bisulfite, ammonium nitrate, and ammonium sulfate, but is not limited to said catalysts. Said catalysts are needed to cure resins based on formaldehyde, which are generally used in the manufacture of all kinds of wood derived boards, fibreboards, particleboards, chipboards, oriented strand boards, and similar. If the formulations of the invention contain one or more catalysts, no further catalysts or formulations containing catalysts need to be used during the curing process.
- compositions of the invention are provided.
- the present invention is related to a hydrophobing and formaldehyde scavenging composition, comprising:
- an O/W suspension or emulsion which as the non-aqueous phase comprises at least one petroleum derived or at least one vegetable derived wax or oil, or a mixture of at least one petroleum derived and at least one vegetable derived wax or oil;
- an aqueous resorcinol solution containing from 35 to 45 wt. % resorcinol; wherein the weight ratio of pure wax with regard to pure resorcinol is between 4:1 and 1 :4, the weight of wax or oil and resorcinol together being between 45 wt.% and 70 wt.% of the composition.
- the weight of wax or oil in the O/W suspension or emulsion is considered, with regard to the weight of resorcinol in the aqueous resorcinol solution.
- the ratio of wax with respect to resorcinol may be, for example, between 3:1 and 1 :3, or between 2,5:1 and 1 :4, or between 2,5:1 and 1 :3, or between 2,5:1 and 1 :2,5, or between 3:1 and 1 :4, or between 4:1 and 3:1 , or between 1 ,5:1 and 1 :1 ,5, or about 1 :1 .
- the weight of wax or oil and resorcinol together means the sum of the weight of wax or oil and the weight of resorcinol; such a weight is defined as being between 45 wt.% and 70 wt.% of the composition, but preferably is between 45 wt.% and 65 wt.%, or between 50 wt.% and 65 wt. %, or between 55 wt.% and 65 wt.%.
- the non-aqueous phase may comprise at least one petroleum derived wax or oil, such as paraffin wax, for example paraffin corresponding to CAS No. 8002-74-2, or slack wax (petroleum), for example as corresponding to CAS No. 64742-61 -6.
- the non-aqueous phase may consist only of one petroleum derived wax or oil, or a mixture of one or more thereof.
- FORESA WAX available to the public from the Spanish company FORESA, S:A: (http://www.foresa.com/en), followed by a four-digit number
- FORESA WAX 2102 the European UFI (https://poisoncentres.echa.europa.eu/es/ufi-generator) for this suspension nowadays is 30001013/1 ).
- FORESA WAX 2102 contains a combination of two types of paraffin, namely about 45 wt% of a paraffin with a low oil content (oil content below 6 wt%, melting point 49-58 °C), and about 1 1 wt.% of a paraffin with high oil content (oil content maximum 12 wt%, melting point 42-53°C), has a solids content of 58-62 wt.% and a pH at 25°C between 8,5 and 10,5.
- the non-aqueous phase may comprise at least one vegetable derived wax or oil, for example palm oil, hydrogenated palm oil or soy oil.
- the non-aqueous phase may consist only of one oil, or of a mixture of 2 or more oils.
- the vegetable oil may be mixed with at least one petroleum derived wax or oil, as defined above.
- the O/W suspension or emulsion comprised in the composition of the invention may comprise from about 1 wt% to 5 wt% of surfactant, the surfactant being one or more selected from anionic and non-ionic surfactants.
- composition according to the invention may comprise up to 25 wt. % of a catalyst for curing formaldehyde derived resins.
- the composition according to the invention may comprise at least one formaldehyde scavenger.
- a formaldehyde scavenger may be selected from, but is not limited to, urea, urea derivatives, urea resins, sodium metabisulfite, ammonium bisulphite, monoethanolamine, and diethanolamine.
- the scavenger may be contained in concentrations, for example, between 0,5 and 20 wt.%, or 0,5 and 15 wt.%, or between 1 and 30 wt.%, or between 1 and 20 wt%, or between 1 and 15 wt.%, or between 2 and 20 wt.%, or between 5 and 20 wt.%, or between 5 and 15 wt.%, among others.
- the O/W suspension or emulsion which is part of the composition of the invention, when the non-aqueous phase is at least one vegetable derived wax or oil, could be, for example, a formulation that comprises an O/W suspension, which comprises:
- surfactant being one or more selected from anionic and non-ionic surfactants, the surfactant being added as such or obtained in situ by addition of between 1 and 2 wt% of an ethanolamine;
- soy oil - from 0 to 8 wt% of soy oil; wherein the total amount of oil, being the sum of palm oil, paraffin and soy oil in the O/W suspension does not exceed 55 wt%; wherein, within the total amount of oils, from 2 to about 10 wt% is non hydrogenated oil, and the rest is hydrogenated and/or partially hydrogenated oil; and wherein the O/W suspension has a solids content of between 30 wt.% and 55 wt.%, and the rest of the suspension, until reaching 100 wt.%, is water, the solids content comprising all the compojnents which are different than water.
- the surfactant of such a formulation may be a mixture of at least one non-ionic surfactant and at least one anionic surfactant.
- Such a formulation may contain up to 25 wt.% of at least one further formaldehyde scavenger, in order to scavenge excess formaldehyde in the formaldehyde based resins, typically used formaldehyde scavengers are urea, monoethanolamine, and diethanolamine, but other formaldehyde scavengers may be used in the formulations of the invention, such as urea, urea derivatives, urea resins, sodium metabisulfite, ammonium bisulphite.
- the composition may contain one or more formaldehyde scavengers, the total amount thereof being up to 25 wt.%, with regard to the total weight of the composition.
- Such a formulation may contain up to 25 wt. % of at least one catalyst for curing formaldehyde based resins; this catalyst, in the frame of the present invention, is meant to be any substance suitable to be used to cure formaldehyde based resins. It may be selected from the group comprising ammonium bisulphite, ammonium nitrate, and ammonium sulphate, but is not limited to said catalysts. Said catalysts are needed to cure resins based on formaldehyde, which are generally used in the manufacture of all kinds of wood derived boards, fibreboards, particleboards, chipboards, oriented strand boards, and similar.
- the composition may contain one or more catalysts for curing formaldehyde based resins, the total amount thereof being up to 25 wt.%, with regard to the total weight of the composition.
- the composition may simultaneously comprise up to 25 wt% of at least one formaldehyde scavenger and up to 25 wt. % of at least one catalyst for curing formaldehyde based resins.
- composition of the invention may be used to increase the hydrophobicity of hydrophilic materials. They may be used, for example, in the manufacture of wood derived boards, fibreboards, particleboards, chipboards, oriented strand boards, fibreglass or rock wool insulations, or combinations thereof, as well as in industrial refining processes of lignocellulosic material.
- composition of the invention may also be used to reduce the formaldehyde emission in materials comprising free formaldehyde, so the legal standards of the final products are met. They may be used, for example, in the manufacture of wood derived boards, fibreboards, particleboards, chipboards, oriented strand boards, or fibreglass or rock wool insulations, or any combinations thereof, as well as in industrial refining processes of lignocellulosic material.
- the indicated materials may comprise a formaldehyde- derived resin or adhesive.
- compositions according to the invention do not only improve the resistance to water of the above mentioned manufactured products, but also reduce the formaldehyde emissions to values which are 0,005 mg of formaldehyde per square meter and hour, or below, as measured by using by using the gas analysis method UNE-EN ISO 12460-3:2016.
- the formaldehyde emission is reduced to values which are 0,004 mg of formaldehyde per square meter and hour, or below, as measured by using by using the gas analysis method UNE-EN ISO 12460-3:2016, or the formaldehyde emission is reduced to values which are 0,003 mg of formaldehyde per square meter and hour, or below, as measured by using by using the gas analysis method UNE-EN ISO 12460-3:2016.
- the invention also refers to wood derived boards, fibreboards, particleboards, chipboards, oriented strand boards, or fibreglass or rock wool insulations, or any combinations thereof, manufactured by using the composition of the invention, which have a formaldehyde emission below 0,005 mg of formaldehyde per square meter and hour as measured by using the gas analysis method UNE-EN ISO 12460-3:2016.
- the formaldehyde emission is 0,004 mg of formaldehyde per square meter and hour, or below, as measured by using by using the gas analysis method UNE-EN ISO 12460-3:2016, or the formaldehyde emission is 0,003 mg of formaldehyde per square meter and hour, or below, as measured by using the gas analysis method UNE-EN ISO 12460-3:2016.
- FORESA WAX 2102 contains a combination of two types of paraffin, namely about 45 wt% of a paraffin with a low oil content (oil content below 6 wt%, melting point 49-58 °C), and about 1 1 % of a paraffin with high oil content (oil content maximum 12 wt%, melting point 42-53°C), has a solids content of 58-62wt% and a pH at 25°C between 8,5 and 10,5.
- FORESA RES 2061 is a water-based melamine-urea-formaldehyde resin
- FORES RES 3250 is a water-based phenol-formaldehyde resin
- intended for the FORESA RES 1350 is a water-based urea-formaldehyde resin, intended for their use in the manufacture of wood-based products and of lignocellulosic composites.
- Example n° 1 Preparation of compositions of the invention comprising resorcinol and hydrogenated vegetable oil emulsion
- the following O/W emulsion was prepared: 175 gr melted hydrogenated palm wax, having an iodine value of ⁇ 10 gr 12/100 gr, 25 gr soy oil and 7 gr of long chain fatty acid were mixed, introduced in an oil phase reactor, and heated to about 70°C, under stirring at about 150 rpm. 275 gr water were introduced in a water phase reactor, 10 gr diethanolamine were added, in order to obtain anionic surfactant in situ by reaction with fatty acids, and the mixture was heated to about 70°C. The oil phase was added to the water phase at a rate of 30 gr/min, and dispersed at a rate of 800 rpm.
- compositions having several different weight ratios of pure vegetable oil with regard to pure resorcinol were prepared, namely: 0:4; 1 :3; 2:2; 3:1 and 4:0.
- the indicated weight ratios refer to pure palm oil and to pure resorcinol, as active substances.
- the mixture was carried out at room temperature by using a disperser, adding the resorcinol solution to the O/W emulsion.
- the shelf life of these samples was greater than one month under storage conditions at room temperature.
- the solids content of the final composition was between 40 wt % and 45 wt %.
- the following O/W emulsion was prepared: In a 4 m 3 reactor, being equipped with a disperser at 120rpm, 1405 kg water were introduced. 30 kg diethanolamine, and subsequently 35 kg of long chain fatty acid, were charged. 100 kg soy oil were charged, together with 0,5 kg of antifoaming agent. Subsequently, 25 kg Tergitol 15-S-9 were added into the reactor. Then 900 kg solid powder of hydrogenated palm wax, having a iodine value of ⁇ 10 gr 12/100 gr, were added, at a rate of 50 kg/min, as well as another 2 kg of antifoaming agent. The mixture is stirred at 120 rpm, during 30 minutes at a temperature of 75 °C.
- compositions having several different weight ratios of pure vegetable oil with regard to pure resorcinol were prepared, namely: 0:4; 1 :3; 2:2; 3:1 and 4:0.
- the indicated weight ratios refer to pure palm oil and to pure resorcinol, as active substances.
- the mixture was carried out at room temperature by the use of a disperser, adding the resorcinol solution to the O/W emulsion.
- the shelf life of these samples was greater than one month under storage conditions at room temperature.
- Example n° 3 Preparation of compositions of the invention comprising resorcinol and hydrogenated vegetable oil emulsion
- the resulting mixture has a Sauter diameter of 1 ,24 microns and a pH of 7,83.
- the final dispersion has a solids content minimum of 60%.
- the obtained emulsion is adjusted by adding water, so that the content of vegetable wax is reduced to 28,57 wt. %.
- the resulting mixture has a Sauter diameter of 1 ,12 microns and a pH of 7,03.
- the manufacture of MDF boards was performed in a pilot plant, using a commercial urea-formaldehyde resin (FORESA RES 1350); the quality results of boards obtained by using the composition of Example n° 3, comprising vegetable oil emulsion and resorcinol, and boards obtained by using the same vegetable oil emulsion but without resorcinol, were compared.
- FRESA RES 1350 commercial urea-formaldehyde resin
- the boards were manufactured in a plate press, with a plate temperature of 200 ° C, the curing factor was 8,5 s / mm, the dose of urea-formaldehyde resin was 12 wt. % dry resin on dry wood fiber and the vegetable oil emulsion dose is always 0,5 wt. % of vegetable oil with respect to dry fiber; that is, the composition of Example n° 3 containing vegetable oil emulsion and resorcinol was dosed in a 1 wt. % dry mix with respect to dry fiber, that is, 0,5 wt.% of vegetable oil and 0,5 wt.% of pure resorcinol.
- MDF boards using the composition according to Example n° 3, or the same vegetable oil emulsion without resorcinol, or a paraffin based commercial emulsion (FORESA WAX 2102) were manufactured.
- the manufacture of MDF board in pilot plant was performed by using a commercial melamine-urea-formaldehyde resin (FORESA RES 2061 ), and the quality results of boards obtained with only the vegetable oil emulsion, i.e. without resorcinol, the composition of Example n° 3, as well as a commercial paraffin-based emulsion were compared.
- FRESA RES 2061 a commercial melamine-urea-formaldehyde resin
- the boards were manufactured in a plate press, with a plate temperature of 200 ° C, the curing factor was 8,5 s / mm, the dose of urea-formaldehyde resin was 12 wt. % of dry resin with respect to dry wood fiber; the hydrofugant emulsion dose was always 0,5 wt. % of vegetable oil or mineral oil with respect to dry fiber; that is, the composition of Example n° 3 was dosed in a 1 wt. % of dry mix with respect to dry fiber, therefore being 0,5 wt. % of hydrogenated palm oil and 0,5 wt. % of pure resorcinol.
- the boards were manufactured in a plate press, with a plate temperature of 200 °C, the curing factor was 8,5 s/mm; the dose of urea-formaldehyde resin was 12 wt. % of dry resin with respect to dry wood fiber, and the waterproofing dose is always 0,5 wt.% of commercial paraffin wax emulsion called FORESA WAX 2102 with respect to dry fiber; also the composition of Example 3 is dosed in a 1 wt.% of dry mix on with respect to dry fiber, being therefore 0,5% of hydrogenated palm oil and 0,5% of pure resorcinol with respect to dry fiber.
- Example n° 3 manages to reduce the emission of the board glued with phenol-formaldehyde resin to values inferior to the natural emission of the wood, taking as reference the pine wood.
- a commercial paraffin based emulsion comprising 60 wt. % solids, being 57,5 wt. % petroleum-derived paraffin wax, 2,5 wt.% of surfactants, at about 25°C, 17,82 gr of water are added, to adjust the solid content to about 30 wt.% of paraffin wax.
- 30 gr solid resorcinol in flakes are added, at room temperature, under stirring, until completely dissolved in the emulsion.
- the final composition obtained comprised 30 wt. % of paraffin wax, 30 wt. % of resorcinol, 38,7 wt. % of water and1 ,3 wt.% surfactants.
- the solid content was 61 ,3 wt.%.
- the resulting mixture has a Sauter diameter of less than 1 micra.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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BR112020019194-9A BR112020019194A2 (en) | 2018-03-23 | 2019-03-22 | HYDROPHOBIC AND SEQUESTRANT COMPOSITIONS OF FORMALDEHYDE UNDERSTANDING WAX AND RESORCINOL EMULSIONS AND THEIR USE TO INCREASE THE HYDROPHOBICITY OF WOODEN COMPOSITE PLATES AND FIBERGLASS INSULATION |
PL19712766.5T PL3768478T3 (en) | 2018-03-23 | 2019-03-22 | Hydrophobing and formaldehyde scavenging compositions comprising wax emulsions and resorcinol and their use for increasing the hydrophobicity of wood composite boards and fibreglass or rock wool insulations |
EP19712766.5A EP3768478B1 (en) | 2018-03-23 | 2019-03-22 | Hydrophobing and formaldehyde scavenging compositions comprising wax emulsions and resorcinol and their use for increasing the hydrophobicity of wood composite boards and fibreglass or rock wool insulations |
ES19712766T ES2922754T3 (en) | 2018-03-23 | 2019-03-22 | Hydrophobic and formaldehyde neutralizing compositions comprising wax and resorcinol emulsions and their use to increase the hydrophobicity of wood composite boards and fiberglass or rock wool insulation |
CONC2020/0011519A CO2020011519A2 (en) | 2018-03-23 | 2020-09-18 | Hydrophobic and formaldehyde-neutralizing compositions comprising wax and resorcinol emulsions and their use to increase the hydrophobicity of wood-composite boards and fiberglass or rock wool insulation |
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EP18382206 | 2018-03-23 | ||
EP18382206.3 | 2018-03-23 |
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WO2019180236A1 true WO2019180236A1 (en) | 2019-09-26 |
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PCT/EP2019/057304 WO2019180236A1 (en) | 2018-03-23 | 2019-03-22 | Hydrophobing and formaldehyde scavenging compositions comprising wax emulsions and resorcinol and their use for increasing the hydrophobicity of wood composite boards and fibreglass or rock wool insulations |
Country Status (7)
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EP (1) | EP3768478B1 (en) |
BR (1) | BR112020019194A2 (en) |
CO (1) | CO2020011519A2 (en) |
ES (1) | ES2922754T3 (en) |
PL (1) | PL3768478T3 (en) |
PT (1) | PT3768478T (en) |
WO (1) | WO2019180236A1 (en) |
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GB2136008A (en) | 1983-02-07 | 1984-09-12 | Enigma Nv | Formaldehyde binder |
US5160679A (en) * | 1989-08-29 | 1992-11-03 | Greene Jack T | Process for making particle board including the use of acetoacetamide as a formaldehyde scavenger |
WO2010054467A1 (en) | 2008-11-12 | 2010-05-20 | Walker Industries Holdings Limited | Wax emulsions incorporating formaldehyde scavengers and methods of preparation thereof |
-
2019
- 2019-03-22 BR BR112020019194-9A patent/BR112020019194A2/en unknown
- 2019-03-22 PL PL19712766.5T patent/PL3768478T3/en unknown
- 2019-03-22 EP EP19712766.5A patent/EP3768478B1/en active Active
- 2019-03-22 PT PT197127665T patent/PT3768478T/en unknown
- 2019-03-22 ES ES19712766T patent/ES2922754T3/en active Active
- 2019-03-22 WO PCT/EP2019/057304 patent/WO2019180236A1/en active Application Filing
-
2020
- 2020-09-18 CO CONC2020/0011519A patent/CO2020011519A2/en unknown
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GB1259470A (en) | 1968-12-19 | 1972-01-05 | ||
GB2136008A (en) | 1983-02-07 | 1984-09-12 | Enigma Nv | Formaldehyde binder |
US5160679A (en) * | 1989-08-29 | 1992-11-03 | Greene Jack T | Process for making particle board including the use of acetoacetamide as a formaldehyde scavenger |
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BR112020019194A2 (en) | 2021-01-05 |
ES2922754T3 (en) | 2022-09-20 |
CO2020011519A2 (en) | 2020-11-20 |
EP3768478A1 (en) | 2021-01-27 |
PT3768478T (en) | 2022-07-20 |
PL3768478T3 (en) | 2022-08-22 |
EP3768478B1 (en) | 2022-04-27 |
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