EP3768478B1 - Émulsions de cire comprenant du résorcinol et leur utilisation dans la fabrication de panneaux dérivés du bois, fibre de verre et de laine de roche - Google Patents

Émulsions de cire comprenant du résorcinol et leur utilisation dans la fabrication de panneaux dérivés du bois, fibre de verre et de laine de roche Download PDF

Info

Publication number
EP3768478B1
EP3768478B1 EP19712766.5A EP19712766A EP3768478B1 EP 3768478 B1 EP3768478 B1 EP 3768478B1 EP 19712766 A EP19712766 A EP 19712766A EP 3768478 B1 EP3768478 B1 EP 3768478B1
Authority
EP
European Patent Office
Prior art keywords
formaldehyde
boards
resorcinol
derived
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP19712766.5A
Other languages
German (de)
English (en)
Other versions
EP3768478A1 (fr
Inventor
José Manuel CASAS PÉREZ
Luis Alberto OTERO VÁZQUEZ
Antonio Sánchez García
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Foresa Technologies SL
Original Assignee
Foresa Technologies SL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foresa Technologies SL filed Critical Foresa Technologies SL
Publication of EP3768478A1 publication Critical patent/EP3768478A1/fr
Application granted granted Critical
Publication of EP3768478B1 publication Critical patent/EP3768478B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4218—Glass fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions

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.
  • the manufacture of fiberglass and rock wool insulation products 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 1B 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
  • 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...In conclusion, the indoor air guide value for formaldehyde is also protective against cancer risk of inhaled formaldehyde" (Ausschuss für iensraumrichthong, 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 für 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).
  • TSCA Title VI provides for quarterly and quality control testing for hardwood plywood, particleboard, and MDF using specified methods developed by ASTM International, among them it is worth noting: ASTM D5582-00 (Reapproved 2006), Standard Test Method for Determining Formaldehyde Levels from Wood Products Using a Desiccator.
  • 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.
  • JIS A 1460:2001 Building boards-Determination of formaldehyde emission-Desiccator method This method describes a method for testing formaldehyde emissions from construction boards by measuring the concentration of formaldehyde absorbed in distilled or deionized water from samples of a specified surface area placed in a glass desiccator for 24 hours.
  • 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
  • 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, 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:
  • 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. Although they do not contain an ionic group as their hydrophilic component, 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. For example, many long chain alcohols exhibit some surfactant properties, such as fatty alcohols, cetyl alcohol, stearyl alcohol, and cetostearyl alcohol, and oleyl alcohol.
  • 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.
  • 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:
  • 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 11 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:
  • 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 11 % 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 I2/100 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 I2/100 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.
  • Example n° 5 Reduction of free formaldehyde content in MDF board manufactured with urea-formaldehyde resin. Vegetable oil emulsion versus composition comprising vegetable oil emulsion and resorcinol.
  • 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.
  • 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 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.
  • Table 4 shows the quality results: Table 4 DENSITY BOARD SANDING CORE BOND WATER RESISTANCE PROPERTIES BOND V-100 THICKN ESS DENS ITY STAND ARD DEVIAT ION DENS ITY BOND INTER NAL BOND STAND ARD DEVIAT ION SWELL ING STAND ARD DEVIAT ION ABSORP TION STAND ARD DEVIAT ION INTER BOND NAL STAND ARD DEVIAT ION mm kg/m 3 ka/m3 ka/m3 N/mm2 N/mm2 % espeso r % peso N/mm2 N/mm2 FORESA WAX 2102 16,01 889 31,71 912 1,57 0,18 4,84 0,19 10,33 0,33 0,33 0,03 VEGETABLE OIL EMULSION 15,98 886 21,66 882 1,84 0,18 5,27 0,02 10,41 1,77 0,30 0,01 COMPOSITION EXAMPLE N° 3 16,00 873 35,96 858 1,82
  • 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.
  • Table 5 shows the quality results: Table 5 DENSITY BOARD SANDING CORE BOND WATER RESISTANCE PROPERTIES BOND V-100 EMISSION THICKNESS DENSITY STAND ARD DEVIATION DENSITY BOND INTERAL BOND STANDARD DEVIATION SWELLING STAND ARD DEVIATION ABSORPTION STAND ARD DEVIATION INTERNAL BOND STANDARD DEVIATION EN 120 mm kg/ m 3 kg/m 3 kg/m 3 N/mm 2 N/mm 2 % % % % N/mm 2 N/m m 2 mg FA/m 2 h FORESA WAX 2102 2,28 843 33,76 850 0,96 0,02 12,08 1,19 42,60 1,13 0,30 0,01 0,0225 COMPOSITI ON EXAMPLE N° 3 2,22 832 16,91 839 0,95 0,003 12,07 0,74 45,86 1,35 0,32 0,01 0,0031
  • 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

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (16)

  1. Composition hydrophobe et de piégeage du formaldéhyde, comprenant :
    - une suspension ou une émulsion H/E, qui, en tant que phase non aqueuse, comprend au moins une cire ou une huile dérivée du pétrole ou au moins une cire ou une huile dérivée d'un végétal, ou un mélange d'au moins une cire ou une huile dérivée du pétrole et d'au moins une cire ou une huile dérivée d'un végétal ; et
    - une solution aqueuse de résorcinol, contenant de 35 à 45 % en poids de résorcinol le rapport pondéral de la cire ou de l'huile par rapport au résorcinol dans la composition étant compris entre 4:1 et 1:4, le poids de la cire ou de l'huile et du résorcinol ensemble étant compris entre 45 % en poids et 70 % en poids de la composition.
  2. Composition selon la revendication 1, dans laquelle le poids de la cire ou de l'huile et du résorcinol ensemble est compris entre 45 % en poids et 65 % en poids de la composition.
  3. Composition selon l'une quelconque des revendications 1 et 2, dans laquelle la phase non aqueuse de la suspension ou de l'émulsion H/E comprend ou consiste en de la paraffine.
  4. Composition selon l'une quelconque des revendications 1 et 2, dans laquelle la phase non aqueuse de la suspension ou de l'émulsion H/E comprend ou consiste en de l'huile de palme.
  5. Composition selon l'une quelconque des revendications précédentes, comprenant de 1 % en poids à 5 % en poids de tensioactif, le tensioactif étant un ou plusieurs éléments choisis parmi les tensioactifs anioniques et non ioniques.
  6. Composition selon l'une quelconque des revendications précédentes, comprenant jusqu'à 25 % en poids d'au moins un catalyseur de durcissement des résines dérivées du formaldéhyde.
  7. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend en outre jusqu'à 25 % en poids d'au moins un piégeur de formaldéhyde.
  8. Composition selon la revendication 7, dans laquelle le piégeur de formaldéhyde est choisi parmi l'urée, les dérivés de l'urée, les résines d'urée, le métabisulfite de sodium, le bisulfite d'ammonium, la monoéthanolamine et la diéthanolamine.
  9. Utilisation d'une composition selon l'une quelconque des revendications précédentes, pour augmenter le caractère hydrophobe de matériaux hydrophiles.
  10. Utilisation d'une composition selon l'une quelconque des revendications 1 à 8, pour réduire le dégagement de formaldéhyde dans des matériaux comprenant du formaldéhyde libre.
  11. Utilisation selon la revendication 9 ou 10, dans laquelle les matériaux sont choisis parmi les panneaux composites en bois, tels que les panneaux dérivés du bois, les panneaux de fibres, les panneaux de particules, les panneaux d'aggloméré, les panneaux à particules orientées, ou les isolants en fibre de verre ou en laine de roche, ou toutes combinaisons de ceux-ci.
  12. Utilisation de la composition selon l'une quelconque des revendications 1 à 8, dans la fabrication de panneaux composites en bois, tels que les panneaux dérivés du bois, les panneaux de fibres, les panneaux de particules, les panneaux d'aggloméré, les panneaux à particules orientées, ou des isolants en fibre de verre ou en laine de roche, ou toutes combinaisons de ceux-ci.
  13. Utilisation selon la revendication 11, dans laquelle les panneaux dérivés du bois, les panneaux de fibres, les panneaux de particules, les panneaux d'aggloméré, les panneaux à particules orientées ou les isolants en fibre de verre ou en laine de roche comprennent une résine ou un adhésif dérivé du formaldéhyde.
  14. Utilisation selon l'une quelconque des revendications 11 à 13, pour réduire le dégagement de formaldéhyde des panneaux composites en bois, tels que les panneaux dérivés du bois, les panneaux de fibres, les panneaux de particules, les panneaux d'aggloméré ou les panneaux à particules orientées ; ou les isolants en fibre de verre ou en laine de roche, à 0,005 mg de formaldéhyde par mètre carré et par heure, ou moins, tel que mesuré par la méthode d'analyse de gaz UNE-EN ISO 12460-3:2016.
  15. Panneaux de bois composite, comprenant une résine ou un adhésif dérivé du formaldéhyde et la composition définie dans les revendications 1 à 8, ayant un dégagement de formaldéhyde de 0,005 mg de formaldéhyde par mètre carré et par heure, ou moins, tel que mesuré par la méthode d'analyse de gaz UNE-EN ISO 12460-3:2016.
  16. Isolants en fibre de verre ou en laine de roche, comprenant une résine ou un adhésif dérivé du formaldéhyde et la composition définie dans les revendications 1 à 8, ayant un dégagement de formaldéhyde de 0,005 mg de formaldéhyde par mètre carré et par heure, ou moins, tel que mesuré par la méthode d'analyse de gaz UNE-EN ISO 12460-3:2016.
EP19712766.5A 2018-03-23 2019-03-22 Émulsions de cire comprenant du résorcinol et leur utilisation dans la fabrication de panneaux dérivés du bois, fibre de verre et de laine de roche Active EP3768478B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18382206 2018-03-23
PCT/EP2019/057304 WO2019180236A1 (fr) 2018-03-23 2019-03-22 Compositions d'hydrophobation et de piégeage de formaldéhyde comprenant des émulsions de cire et du résorcinol et leur utilisation pour augmenter l'hydrophobicité de panneaux composites de bois et d'isolations en fibre de verre ou en laine de roche

Publications (2)

Publication Number Publication Date
EP3768478A1 EP3768478A1 (fr) 2021-01-27
EP3768478B1 true EP3768478B1 (fr) 2022-04-27

Family

ID=62002608

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19712766.5A Active EP3768478B1 (fr) 2018-03-23 2019-03-22 Émulsions de cire comprenant du résorcinol et leur utilisation dans la fabrication de panneaux dérivés du bois, fibre de verre et de laine de roche

Country Status (7)

Country Link
EP (1) EP3768478B1 (fr)
CO (1) CO2020011519A2 (fr)
ES (1) ES2922754T3 (fr)
MY (1) MY204908A (fr)
PL (1) PL3768478T3 (fr)
PT (1) PT3768478T (fr)
WO (1) WO2019180236A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026087821A1 (fr) * 2024-10-25 2026-04-30 Upm-Kymmene Corporation Inhibiteur d'émission

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114904380A (zh) * 2022-05-30 2022-08-16 皇苹果家居用品集团有限公司 一种生物降解甲醛清除剂
JP7628265B1 (ja) 2024-06-21 2025-02-10 旭ファイバーグラス株式会社 無機繊維断熱吸音材用水性バインダーの製造方法
FI20246272A1 (en) * 2024-10-25 2026-04-26 Upm Kymmene Corp Emission inhibitor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1595250A (fr) 1968-12-19 1970-06-08
GB2136008B (en) 1983-02-07 1986-06-25 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 (fr) 2008-11-12 2010-05-20 Walker Industries Holdings Limited Émulsions de cire comportant des capteurs de formaldéhyde et leurs procédés de préparation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026087821A1 (fr) * 2024-10-25 2026-04-30 Upm-Kymmene Corporation Inhibiteur d'émission

Also Published As

Publication number Publication date
BR112020019194A2 (pt) 2021-01-05
MY204908A (en) 2024-09-20
PT3768478T (pt) 2022-07-20
PL3768478T3 (pl) 2022-08-22
ES2922754T3 (es) 2022-09-20
EP3768478A1 (fr) 2021-01-27
WO2019180236A1 (fr) 2019-09-26
CO2020011519A2 (es) 2020-11-20

Similar Documents

Publication Publication Date Title
US8084523B2 (en) Processes and manufacturing methods to produce an aqueous thermosetting fire-rated fire-retardant polymeric adhesive composition for manufacturing interior or exterior fire-rated cellulosic products
EP3768478A1 (fr) Compositions d'hydrophobation et de piégeage de formaldéhyde comprenant des émulsions de cire et du résorcinol et leur utilisation pour augmenter l'hydrophobicité de panneaux composites de bois et d'isolations en fibre de verre ou en laine de roche
CA2197141C (fr) Compositions lignocellulosiques a forte charge en borate
Baharoğlu et al. Effects of anatomical and chemical properties of wood on the quality of particleboard
EP2346682B1 (fr) Corps moulés multicouches contenant de la lignocellulose, à faible émission de formaldéhyde
AU2009262835B8 (en) Storage stable melamine-urea-formaldehyde resins and applications thereof
EP2447332A1 (fr) Colle hybride et son utilisation dans des plaques en bois
EP3768510B1 (fr) Composition adhésive monocomposant comprenant une résine à base de formaldéhyde ayant une teneur en formaldéhyde libre inférieure à 0,1 wt%, comprenant du résorcinol, d'alkylrésorcinol et/ou du tanin
WO2010054467A1 (fr) Émulsions de cire comportant des capteurs de formaldéhyde et leurs procédés de préparation
Sarı et al. Effects of chemical composition of wood and resin type on properties of particleboard
CA2547751A1 (fr) Emulsion de cire pour fabriquer des panneaux composites
Ghani et al. Addition of propylamine as formaldehyde scavenger for urea formaldehyde-bonded particleboard
DE19843493A1 (de) Werkstoff aus Holzspänen und Bindemitteln für einen Einsatz im Bauwesen und Möbelbau sowie Verfahren zu seiner Herstellung
Islam et al. Raw natural rubber latex-based bio-adhesive for the production of particleboard: formulation and optimization of process parameters
Musbah Redwan et al. The effect of aluminium hydroxide (ATH) on the mechanical properties and fire resistivity of palm-based fibreboard prepared by pre-polymerization method
EP3067402B1 (fr) Composition de liant et son utilisation dans des panneaux en dérivé de bois
US4012558A (en) Process for the manufacture of flame-resistant boards, a flame-retardant mixture and a flame-retardant bonding composition containing the same
Asafu-Adjaye et al. Soy flour substitution in polymeric methylene diphenyl diisocyanate resin for composite panel applications
Wang et al. Manufacturing medium-density particleboards from wood–bark mixture and different adhesive systems
BR112020019194B1 (pt) Composições hidrofóbicas e sequestrantes de formaldeído compreendendo emulsões de cera e resorcinol e seu uso para aumentar a hidrofobicidade de placas compósitas de madeira e isolamentos de lã de pedra e fibra de vidro
EP3519505B1 (fr) Formulations h/e à base d'huile végétale issues de matières renouvables pour augmenter l'hydrophobicité de plaques de matériaux dérivé du bois, d'isolation de fibre en verre ou de panneaux isolants en laine
Tan The use of p-MDI resin in MDF manufacture
DE102010064103A1 (de) Dämmmaterial
EP2528958A1 (fr) Résines amino-formaldéhyde, leurs applications et articles fabriqués à partir de celles-ci
DE102013014641B4 (de) Holzwerkstoffprodukt oder Naturfaser-Verbundwerkstoffprodukt und Verwendung eines formaldehydfreien Aminoplastharzes zu deren Herstellung

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200917

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20210810

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SANCHEZ GARCIA, ANTONIO

Inventor name: OTERO VAZQUEZ, LUIS ALBERTO

Inventor name: CASAS PEREZ, JOSE MANUEL

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20220103

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1486591

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602019014155

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Ref document number: 3768478

Country of ref document: PT

Date of ref document: 20220720

Kind code of ref document: T

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20220715

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20220427

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1486591

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220427

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2922754

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20220920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220728

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220827

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602019014155

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

26N No opposition filed

Effective date: 20230130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230524

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230322

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230322

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230322

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250327

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20250319

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20250401

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20190322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20190322

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20251215

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20251215

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20260330

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20260310

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20260305

Year of fee payment: 8