Aromatic polyol stabilized resole resin

Abstract

Providing stabilized resole resins. The present invention relates to a stabilized resole resin comprising water, a water-soluble aminophenol resin, and a water-soluble aromatic polyol as a solubilizer for the water-soluble aminophenol resin. The present invention also relates to a diluted aqueous binder composition containing the stabilized resole resin and additives, and a method for producing a fiber insulation product using the aqueous binder composition.

Description

[Technical Field]

[0001] The present invention relates to an aminoresol resin stabilized with a solubilizer selected from water-soluble aromatic polyols, an aqueous binder composition prepared from this resin, a method for producing insulation products based on fibers, especially mineral wool, using this aqueous binder composition, and the heat and / or sound insulation products obtained by this method. The use of a water-soluble polyhydroxylated aromatic compound as a solubilizer or cosolvent for the resin makes it possible to partially or completely replace urea, which is commonly used in this type of resin. [Background technology]

[0002] The production of mineral wool-based insulation products typically involves producing glass or rock fibers by a centrifugal process (fiberization). On its path between the centrifugal device and the fiber collection belt, an aqueous binder composition, also called a sizing composition, is sprayed onto the still-hot fibers, which then undergo a thermal curing reaction at a temperature of about 200°C.

[0003] The aqueous binder composition is prepared immediately before use by diluting the concentrated thermosetting resin with water and adding various commonly used additives (coupling agents, anti-dusting agents, hydrophobic agents, catalysts).

[0004] Concentrated thermosetting resins must be storage stable, i.e., they must not precipitate and must retain their ability to be diluted with water to prepare sizing compositions for as long as possible. A thermosetting resin is generally considered stable if, after a storage period of at least 14 days at a temperature of 12-18°C, it remains in solution without precipitate and retains at least 1000% dilutability (1 volume of resin plus 9 volumes of water gives a clear solution without permanent haze).

[0005] Furthermore, from a regulatory point of view, the resin should be considered non-polluting, i.e., it should contain the smallest possible amount of compounds that may be harmful to human health or the environment, and should produce the smallest possible amount of such compounds during use of the resin.

[0006] The most commonly used thermosetting resins are phenolic resins of the resole type. In the technical field of phenol-formaldehyde resins, two main families are distinguished: novolac resins prepared in an acidic medium, and - resols obtained by basic catalysis.

[0007] The phenolic resins of the present invention belong to this second family.

[0008] Resole resins are obtained by the reaction of phenol with excess formaldehyde in a basic medium; the formaldehyde / phenol molar ratio is typically 2 to 4, so that each molecule of phenol can potentially react with three molecules of formaldehyde.

[0009] The resole resins thus obtained contain numerous methylol functional groups on the aromatic rings, which constitute the sites for crosslinking by dehydration / formol release. These resins essentially consist of phenol / formaldehyde (PF) condensates, residual phenol, and residual formaldehyde. They react in acidic media, i.e., they polymerize and precipitate very rapidly at ambient temperature.

[0010] To reduce the amount of residual formaldehyde and improve the storage stability of resins, it has been proposed to first add a sufficient amount of urea to the resin after neutralization of the catalyst to react with the liberated residual formaldehyde and form a urea-formaldehyde (UF) condensate. Therefore, such resins contain phenol-formaldehyde (PF) and urea-formaldehyde (PF) condensates. Nevertheless, these resins were found to release formaldehyde during the crosslinking step due to thermal decomposition of the urea-formaldehyde condensates. Formaldehyde was also released from the final product during its use as a heat and / or sound insulator. Such urea-treated resols and their preparation are described in detail in International Application WO 01 / 96254.

[0011] Several years ago, the applicant proposed improved resole resins (hereinafter equivalently referred to as "amino resins" or "aminophenol resins") that are storage stable and substantially free of urea-formaldehyde (UF) resins.

[0012] These aminophenol resins are water-soluble resins that are stable at acidic pH, even at very acidic pHs of 1 to 2. This good stability is obtained by an additional reaction step, which consists in reacting a resole consisting essentially of a phenol / formaldehyde condensate, phenol, and formaldehyde, with an amine, preferably a monoalkanolamine, especially monoethanolamine.

[0013] The alkanolamine reacts with phenol / formaldehyde (PF) condensates according to the Mannich reaction, reacting with the remaining phenol and formaldehyde to form phenol / formaldehyde / amine (PFA) condensates. At the end of the reaction, the reaction mixture can be acidified at ambient temperature without polymerization. Therefore, these aminoresoles are considered stable in acidic media. Their synthesis is described in WO 2008 / 043960 and WO 2008 / 043961 by the applicant. They are further distinguished by the absence of urea-formaldehyde condensates. As explained above, these undesirable UF condensates are present in large amounts in many prior art phenolic resins, which have insufficient thermal stability and release formaldehyde upon thermal decomposition.

[0014] In known methods, after reaction with monoalkanolamine, cooling of the reaction mixture, and acidification, up to 25% by weight, preferably 10% to 20% by weight, of urea can be added to the aminophenol resin, these amounts being expressed relative to the total dry weight of the aminoresole. In this case, urea primarily acts as a cosolvent or solubilizer, further reducing the cost of the sizing composition and the resulting product. Urea also removes traces (less than 0.2%) of formaldehyde that may still be present at the end of the synthesis.

[0015] Thus, aminophenol resins, in aqueous solutions stabilized by urea (solubilizer), have been used by the applicant for more than 10 years for the manufacture of mineral fiber-based insulation products, which emit very low amounts of formaldehyde during manufacture and use.

[0016] The only drawback of these resins lies in the fact that ammonia (NH3), a product of the thermal decomposition of urea, is formed during the thermal curing step at the manufacturing site and also, to a lesser extent, during use. Summary of the Invention

[0017] The aim of the present invention was to propose a solubilizer or cosolvent different from urea, which: - capable of stabilizing aqueous solutions of aminophenol-formaldehyde resins at least as efficiently as urea (without crystals and at a dilution of more than 1000% for at least 14 days); - When exposed to temperatures required for curing resole resins, typically 180-230°C, they do not release ammonia or any other harmful substances; - Preferably not classified as a carcinogenic, mutagenic, or toxic to reproduction (CMR) chemical. DETAILED DESCRIPTION OF THE INVENTION

[0018] The applicant has tested a large number of organic compounds, in particular amino acids, (poly)aldehydes, aromatic and non-aromatic polyols, and hydrocarbons, but only water-soluble aromatic polyols have proven to be sufficiently effective to stabilize aminophenol resins in concentrated aqueous solutions for at least 14 days.

[0019] The inventors have observed that some polyhydroxylated aromatic compounds are more effective stabilizers than urea, making it possible to reduce their usage and at least partially compensate for the higher cost of these compounds compared to the cost of urea.

[0020] The subject of the present invention is therefore a stabilized resole resin comprising: (a) water, (b) a water-soluble aminophenol resin, preferably a water-soluble aminophenol resin consisting essentially of a phenol-formaldehyde (PF) condensate and a phenol-formaldehyde-amine (PFA) condensate; and (c) Water-soluble aromatic polyols as solubilizers for water-soluble aminophenol resins.

[0021] Another subject of the present invention is an aqueous binder composition prepared from the stabilized resole resin by dilution and the addition of common additives. This aqueous binder composition thus comprises water (for dilution), the stabilized resole resin as defined above, and one or more additives selected from coupling agents, anti-dusting oils or emulsions, hydrophobic agents, and curing accelerators.

[0022] Finally, the subject of the present invention is a method for producing an insulation product based on organic or mineral fibers using an aqueous binder composition, and also the insulation product obtained by this method, the organic or mineral fibers being bound together by an insoluble, infusible binder obtained by hardening of the components of the aqueous binder composition.

[0023] Throughout the description of the invention, it is necessary to distinguish between: aminophenolic resins, which are obtained by condensation of phenols, formaldehyde and amines in a basic medium and do not contain urea-formaldehyde (UF) condensates; stabilized resole resins, which contain aminophenol resins, water, and solubilizers; and - Binder compositions prepared by diluting the stabilized resole resins and adding known additives such as coupling agents, anti-dusting agents, hydrophobic agents, and catalysts or accelerators.

[0024] Thus, stabilized resole resins are concentrated resins obtained from synthesis that are stored, transported, sold, and used as a thermosetting component for the preparation of aqueous binder compositions immediately prior to carrying out the manufacturing process.

[0025] It is advantageously - 75 to 99% by weight, preferably 80 to 97% by weight, in particular 85 to 95% by weight, of a water-soluble aminophenol resin, and 1 to 25% by weight, preferably 3 to 20% by weight, in particular 5 to 15% by weight, of a water-soluble aromatic polyol Contains:

[0026] These percentages are based on the total dry weight of the stabilized resole resin.

[0027] The water content is usually 30 to 60% by mass, preferably 35 to 55% by mass, and particularly 40 to 50% by mass.

[0028] The phrase "water-soluble aromatic polyol" used to describe the solubilizer includes both the pure compound used alone and mixtures of two or more water-soluble aromatic polyols.

[0029] The resin also contains a small amount of salt at the end of the resin synthesis resulting from neutralization of the catalyst (a strong base such as NaOH or KOH) with an acid, for example sulfamic acid.

[0030] In the present invention, the adjective "stabilized" in reference to a resole resin means that the resin remains in the form of a clear solution without precipitate during storage for at least 14 days at a temperature of 12-18°C, and during this period it retains at least 1000% dilutability in water.

[0031] The solubilizers used in the present invention to at least partially replace the previously used urea are selected from water-soluble aromatic polyols, which are preferably not carcinogenic, mutagenic or reproductively toxic (CMR) chemicals. The list of CMR compounds is that set out in Annex VI of EC Regulation No 1272 / 2008.

[0032] In the present case, a water-soluble aromatic polyol is considered to be one having a solubility in water at 20°C of more than 20 g / l, preferably more than 50 g / l.

[0033] Aromaticity is an important aspect of the solubilizers used in the present invention. In fact, the applicant has tested several non-aromatic polyhydroxylated compounds that are indeed water-soluble and not classified as CMRs, such as glycerol, carbohydrates, and hydrogenated sugars (alditols), but they are ineffective in stabilizing phenolic resins, i.e., maintaining the dilutability of the resin during storage for at least 14 days at temperatures between 12 and 18°C, and preventing its crystallization when stored at low temperatures (3°C). The aromaticity of polyols will increase their affinity for phenolic resins, which are themselves aromatic, and therefore increase the solubility of the phenolic resins in water.

[0034] The solubilizer used in the present invention contains at least two hydroxyl groups. The hydroxyl groups are preferably located directly on the aromatic ring. The solubilizer can contain a monocyclic aromatic ring (benzene) or a polycyclic aromatic ring (naphthalene, anthracene). It is advantageously monocyclic or bicyclic, preferably monocyclic, and has at least two, preferably two or three, hydroxyl functional groups located directly on the aromatic ring.

[0035] Examples of polyhydroxylated aromatic compounds that may be used as solubilizers in the present invention include unsubstituted polyphenols such as resorcinol, phloroglucinol, and pyrocatechol, substituted polyphenols having aldehyde, carboxylic acid, alkyl, and ether substituents, such as gallic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dihydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 4-methoxybenzene-1,2-diol, 4-methoxybenzene-1,3-diol, and mixtures thereof.

[0036] Among these compounds, resorcinol and phloroglucinol are particularly preferred. In fact, these compounds can both solubilize the aminophenol resin in water and remove traces (less than 0.2%) of free formaldehyde that may be present in the aminophenol resin at the end of synthesis. In fact, as is known, resorcinol and phloroglucinol can react with formaldehyde to form aromatic compounds having one or more methylol functional groups, which can react with the condensation products of PF and PFA of the phenol resin.

[0037] If the water-soluble aromatic polyol(s) used can react with formaldehyde, the addition of urea to the resole resin is in principle unnecessary, and the stabilized resole resin of the present invention is therefore preferably urea-free. In fact, the complete absence of urea ensures the absence of ammonia (NH3) emissions during the step of thermal curing of the binder and during use of the produced insulation product.

[0038] When a solubilizing agent that, unlike resorcinol, cannot remove traces of formaldehyde is used, it may be useful to add a small amount of urea to the resole resin to be stabilized. This addition may be carried out before or after the addition of the polyhydroxylated aromatic solubilizing agent, but should be carried out after the synthesis of the aminophenol resin consisting essentially of PF and PFA condensates is complete, i.e., after the reaction solution has been cooled and neutralized. In fact, it is necessary to prevent the formation of urea-formaldehyde condensates during the synthesis of the resin.

[0039] Although it is technically possible according to the invention to completely dispense with urea, the addition of the latter to resole resins remains advantageous from an economic point of view in many cases.

[0040] When both urea and a water-soluble aromatic polyol are utilized as solubilizers, the resin advantageously contains less than 15% by weight, such as 0.1 to 15% by weight, preferably less than 10% by weight, such as 0.5 to 10% by weight, in particular less than 5% by weight, such as 1 to 5% by weight, of urea, based on the total dry weight (aminophenol resin + aromatic polyol + urea) of the stabilized resole resin.

[0041] Therefore, the mass ratio of urea to aromatic polyol is usually 1 / 4 to 3 / 1, preferably 1 / 3 to 2 / 1, and particularly 1 / 2 to 1.

[0042] The phenolic resins used in the present invention contain basic (protonatable) amine functional groups and are stable in acidic media.

[0043] These phenolic resins containing amine functional groups are known, and their preparation has been described in detail by the applicant in WO 2008 / 043960 and WO 2008 / 043961. They consist essentially of phenol / formaldehyde (PF) condensates and phenol / formaldehyde / amine (PFA) condensates, and are distinguished in particular by the absence of urea-formaldehyde (UF) condensates. As explained at the beginning, these urea-formaldehyde condensates, present in large amounts in many other phenolic resins of the prior art, have insufficient thermal stability, and release formaldehyde and ammonia upon thermal decomposition.

[0044] The stabilized resole resins of the invention advantageously have a pH of between 1.0 and 6.5, preferably between 1.5 and 5.5, and more preferentially between 1.6 and 5.0.

[0045] Aqueous binder compositions prepared by diluting the stabilized resole resin with water usually have a less acidic pH than the resole resin, typically from 3 to 7, especially from 3.5 to 6.5, which is advantageous for preventing corrosion in facilities for manufacturing insulation products. The dilution water used to prepare binder compositions from stabilized resole resins may be derived in part from recycled wash water from facilities for manufacturing insulation products.

[0046] Thus, the present binder composition contains water, a stabilized resole resin, and one or more additives commonly used in the field of mineral wool based insulation products.

[0047] These additives are chosen, inter alia, from coupling agents, in particular functional silanes such as aminosilanes or epoxysilanes, anti-dusting oils or emulsions, in particular mineral oils, hydrophobic agents such as reactive or non-reactive polyorganosiloxanes (silicones), and accelerators for the curing reaction.

[0048] At the time of application to the fibers, the binder composition preferably has a solids content of 2 to 25% by weight, preferably 3 to 15% by weight, and therefore contains 75 to 98% by weight, in particular 85 to 97% by weight, of water.

[0049] In a preferred embodiment, the aqueous binder composition is urea-free.

[0050] The binder composition is applied in such an amount that the content of insoluble, infusible binder in the final product obtained after heat curing is 2% to 20% by weight, preferably 3% to 15% by weight, in particular 4 to 12% by weight.

[0051] Another subject of the present invention is a method for producing an insulating product based on mineral or organic fibers, which method comprises the following successive steps: - applying the aqueous binder composition according to the invention to mineral or organic fibers, preferably to mineral fibers; and - Heating fibers bound with an aqueous binder composition so as to evaporate the volatile phase of the aqueous binder composition and to bring about thermal curing of the non-volatile residue, or packaging mineral or organic fibers bound with an uncured aqueous binder composition for storage and / or transport purposes.

[0052] The mineral fibres are advantageously chosen from mineral wool fibres, in particular glass wool or rock wool.

[0053] If the insulation product is based on mineral wool, the binder composition is projected by spraying onto the mineral fibers at the outlet of the centrifugal device (fiberization), after which the mineral fibers are collected in the form of a fiber layer on a receiving element (molding) and then treated in an oven at a temperature that allows crosslinking of the reactive components and the formation of an infusible binder (curing). This crosslinking / thermosetting step is carried out by heating to a temperature of 180°C or higher, preferably 190°C to 220°C, for 20 to 300 seconds, preferably 30 to 250 seconds.

[0054] When the insulation product is based on organic fibers, such as fibers of plant origin (e.g., cellulose fibers) or fibers of animal origin such as wool, the curing temperature is typically lower than that used for curing products based on mineral fibers, to protect the organic fibers from potential thermal decomposition. The curing temperature is, for example, 150 to 200°C. The curing time is typically several minutes to several tens of minutes, for example, 5 to 50 minutes, and preferably 10 to 30 minutes.

[0055] In the method of the present invention, curing of the mineral or organic fibers can be carried out by applying the binder composition to the fibers and collecting the bonded fibers on a conveyor belt, immediately followed by passing the fibers through, for example, a temperature-controlled oven at the desired curing temperature.

[0056] The present method further contemplates a curing step that is separate from the steps of manufacturing the bonded fiber mat, and includes embodiments in which the bonded fiber mat is packaged rather than immediately cured, e.g., partially dried, cut, compressed, molded, and wrapped.

[0057] The packaging material should be selected to allow these intermediate products (fibers bound with uncured binder) to be stored and / or transported with a view to additional steps, including heat curing of the binder, which may be carried out later or elsewhere, for example after optionally shaping the intermediate product in a mold.

[0058] The packaging material is preferably a plastic film. [Example]

[0059] example Synthesis of unstabilized resole resins 380 g of phenol (4 mol), 313 g of paraformaldehyde (10 mol) used as formaldehyde source, and 367 g of water (paraformaldehyde / phenol molar ratio equal to 2.5) are introduced into a 2 liter reactor equipped with a stirring system and with a condenser at the top, and the mixture is heated to 45°C while stirring.

[0060] 53.2 g of 50% sodium hydroxide solution (7% by weight relative to the phenol) are then added regularly over 30 minutes, then the temperature is gradually raised to 70° C. in 30 minutes and maintained for 80 minutes.

[0061] The temperature is then gradually reduced to 60°C over 30 minutes, while 71.5 g of monoethanolamine (1.17 mol) is added periodically to the reaction mixture. The temperature is maintained at 60°C for 15 minutes, the mixture is cooled to about 35°C in 30 minutes, and sulfamic acid is added in 60 minutes until the pH is equal to 5.0. The pH is then reduced to 4.5 using a 15% sulfamic acid solution. If necessary, the mass content of solids in the liquid resin is adjusted to 58% with water.

[0062] The resin obtained has the appearance of a clear aqueous composition: it has a free formaldehyde content equal to 0.1%, a free phenol content equal to 0.5% (these contents expressed relative to the total mass of the liquid), and a dilutability greater than 2000%. It is called an unstabilized resole resin.

[0063] Preparation of stabilized resole resins The unstabilized resole resin is divided into batches, and the stabilizer to be tested is added to each batch in an amount equal to 20 parts per 80 parts dry weight of the resin for those with sufficient solubility, or 10 parts by weight per 80 parts dry weight of the unstabilized resole resin for those with insufficient solubility (see Table 1). Stirring is carried out at ambient temperature until complete dissolution is achieved, so that the so-called "stabilized" resole resin is obtained, the stability of which is evaluated.

[0064] Additionally, two batches of stabilized resole resin are prepared under the same conditions by adding 5 parts resorcinol and 5 parts phloroglucinol to 80 parts unstabilized resole resin, respectively.

[0065] Dilutability The dilutability of various resole resins over time is evaluated. The resins are prepared in the following manner: 10 ml of resin is poured into a 250 ml Erlenmeyer flask. 10 ml of water is added, the mixture is stirred, and it is determined whether a cloudiness appears. If the solution remains clear, another 10 ml of water is added, and the clarity of the solution is evaluated again. This cycle is repeated until a permanent cloudiness appears (dilutability = (number of additions + 1) x 100), or until 10 ml of water has been added 19 times without a cloudiness appearing. In the latter case, the resin has a dilutability of 2000%, which means it can be diluted infinitely.

[0066] Crystallization stability To evaluate the crystallization stability of resole resins, 20 ml of resin is poured into glass tablet organizers and stored at 3° C., inspecting them at regular intervals for the appearance or absence of crystals. Crystallization stability is defined as the number of days of storage at 3° C. without the appearance of white crystals at the bottom of the tablet organizer.

[0067] Free formaldehyde content Additionally, the free formaldehyde content of the resole resin is evaluated to determine the ability of the stabilizer to react with residual formol (formaldehyde scavenging function).

[0068] For this purpose, approximately 1 g of resol resin is placed in a 100 ml volumetric flask and the mass m of the sample is accurately recorded. Distilled water is added up to the mark. The formol content is determined using a LANGE DR6000 colorimeter equipped with an LCK 325 Formol Quantification Kit according to the manufacturer's instructions.

[0069] The measurement is carried out on a 1 ml sample taken in a preparative flask. The result A obtained by the colorimeter is given in mg / l. The free formaldehyde content is calculated as follows: % Free Formaldehyde = (A x 0.1) / m x 100

[0070] Free formaldehyde content is given as a % of the sample, expressed to ±0.01%. Any result less than 0.01% will be indicated as <0.01%.

[0071] Ammonia excretion Finally, ammonia emissions during the curing of various resole resins are evaluated by conducting a contamination simulation in the laboratory. A resole resin solution equivalent to 1 g of solids, pre-diluted to a solids content of 30%, is introduced into a 1 L flat-bottom glass flask. The inlet of a dipper is connected to this flat-bottom flask, and an air flow rate of 1 L / min is used to sweep the surface of the sample. The assembly is placed in a ventilated oven preheated to 215 °C. The outlet of the dipper is connected to three bubblers, each containing 100 ml of 0.02 N sulfuric acid solution, arranged in series outside the oven. After 1 hour of curing, the contents of the bubblers are analyzed by ion chromatography to quantify the amount of ammonia removed.

[0072] The results are collated in Table 1 below for all substances tested as stabilizers, which may be potential candidates for replacing urea. [Table 1]

[0073] Of all the organic compounds evaluated, only resorcinol and phloroglucinol have a resole resin stabilizing power at least equal to or greater than that of urea: in fact, greater than 1000% dilutability and crystallization stability are observed over comparable or longer periods.

[0074] Resorcinol and phloroglucinol, like urea, can also react with the free formaldehyde contained in unstabilized resole resins. When comparing resorcinol and phloroglucinol with urea, a significant reduction in ammonia emissions is observed (310 mg / m 3 to 20 mg / m 3less than). The present disclosure includes the following inventive aspects: <Aspect 1> - water, - water-soluble aminophenol resins, and a water-soluble aromatic polyol as a solubilizer for the water-soluble aminophenol resin; 1. A stabilized resole resin comprising: <Aspect 2> from 75 to 99% by weight, preferably from 80 to 97% by weight, in particular from 85 to 95% by weight, of a water-soluble aminophenol resin, 1 to 25% by weight, preferably 3 to 20% by weight, in particular 5 to 15% by weight, of a water-soluble aromatic polyol Contains 2. The stabilized resole resin of embodiment 1, wherein these percentages are based on the total dry weight of the stabilized resole resin. <Aspect 3> 3. The stabilized resole resin of claim 1 or 2, wherein the water-soluble aromatic polyol is a compound comprising a monocyclic or bicyclic, preferably monocyclic, aromatic ring having at least two hydroxyl functional groups directly positioned on the aromatic ring. <Aspect 4> 4. The stabilized resole resin of claim 3, wherein the water soluble aromatic polyol is selected from the group consisting of resorcinol, phloroglucinol, pyrocatechol, gallic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dihydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 4-methoxybenzene-1,2-diol, 4-methoxybenzene-1,3-diol, and mixtures of these compounds. <Aspect 5> 5. The stabilized resole resin of aspect 4, wherein the water-soluble aromatic polyol is selected from the group consisting of resorcinol and phloroglucinol. <Aspect 6> 6. The stabilized resole resin of any one of aspects 1 to 5, further comprising 0.1 to 15%, preferably 0.5 to 10%, and in particular 1 to 5%, by weight of urea, based on the total dry weight of the stabilized resole resin. <Aspect 7> Aspect 6. The stabilized resole resin of any one of aspects 1 to 5, which is urea-free. <Aspect 8> Aspect 8. The stabilized resole resin of any one of aspects 1 to 7, wherein the water-soluble aminophenol resin consists essentially of a phenol-formaldehyde condensate and a phenol-formaldehyde-amine condensate. <Aspect 9> A stabilized resole resin according to any one of the preceding aspects, having a pH of 1.0 to 6.5, preferably 1.5 to 5.5, more preferentially 1.6 to 5.0. <Aspect 10> 10. An aqueous binder composition comprising: water; the stabilized resole resin of any one of embodiments 1 to 9; and one or more additives selected from a coupling agent, an anti-dusting oil or emulsion, a hydrophobic agent, and a cure accelerator. <Aspect 11> 11. The aqueous binder composition according to embodiment 10, comprising 75 to 98% by weight of water. <Aspect 12> 12. The aqueous binder composition of claim 10 or 11, which is urea-free. <Aspect 13> - applying an aqueous binder composition according to any one of aspects 10 to 12 to mineral or organic fibres, preferably mineral fibres; and - heating the fibers bound with the aqueous binder composition to evaporate the volatile phase of the aqueous binder composition and to effect thermal curing of the non-volatile residue, or packaging the mineral fibers or organic fibers bound with the uncured aqueous binder composition for storage and / or transportation purposes. 1. A method for producing an insulation product based on mineral or organic fibers, comprising: <Aspect 14> 14. The method according to aspect 13, wherein the mineral fibers are selected from mineral wool fibers, in particular glass wool fibers or rock wool fibers. <Aspect 15> 15. A mineral or organic fiber based insulation product obtainable by the method according to aspect 13 or 14.

Claims

1. - water, - water-soluble aminophenol resins, and a water-soluble aromatic polyol as a solubilizer for the water-soluble aminophenol resin; A stabilized resole resin comprising: the stabilized resole resin has a pH of 1.0 to 6.5; Stabilized resole resin.

2. - 75 to 99% by weight of a water-soluble aminophenol resin, - 1 to 25% by weight of a water-soluble aromatic polyol Contains 10. The stabilized resole resin of claim 1, wherein these percentages are based on the total dry weight of the stabilized resole resin.

3. 3. The stabilized resole resin of claim 1, wherein the water-soluble aromatic polyol is a compound containing a monocyclic or bicyclic aromatic ring having at least two hydroxyl functional groups directly positioned on the aromatic ring.

4. 4. The stabilized resole resin of claim 3, wherein the water-soluble aromatic polyol is selected from the group consisting of resorcinol, phloroglucinol, pyrocatechol, gallic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dihydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 4-methoxybenzene-1,2-diol, 4-methoxybenzene-1,3-diol, and mixtures of these compounds.

5. 5. The stabilized resole resin of claim 4, wherein the water-soluble aromatic polyol is selected from the group consisting of resorcinol and phloroglucinol.

6. The stabilized resole resin of any one of claims 1 to 5, further comprising 0.1 to 15 wt% urea, based on the total dry weight of the stabilized resole resin.

7. The stabilized resole resin of any one of claims 1 to 5, which is urea-free.

8. The stabilized resole resin of any one of claims 1 to 7, wherein the water-soluble aminophenol resin consists essentially of a phenol-formaldehyde condensate and a phenol-formaldehyde-amine condensate.

9. 9. An aqueous binder composition comprising water, the stabilized resole resin of claim 1, and one or more additives selected from a coupling agent, an anti-dusting oil or emulsion, a hydrophobic agent, and a curing reaction accelerator.

10. 10. The aqueous binder composition of claim 9, containing 75 to 98% by weight of water.

11. 11. The aqueous binder composition of claim 9 or 10, which is urea-free.

12. - applying an aqueous binder composition according to any one of claims 9 to 11 to mineral or organic fibres, and - heating the fibers bound with the aqueous binder composition so as to evaporate the volatile phase of the aqueous binder composition and to bring about thermal curing of the non-volatile residue, or packaging the mineral fibers or the organic fibers bound with the uncured aqueous binder composition for storage and / or transport purposes.

1. A method for producing an insulation product based on mineral or organic fibers, comprising:

13. 13. The method of claim 12, wherein the mineral fibers are selected from mineral wool fibers.

Images