Mineral wool binders based on phenolic resins and carbohydrates

Abstract

The invention relates to an aqueous binder composition for mineral wool fibers, made from a mixture of I) a phenol-urea-formaldehyde binder (PUF binder), and II) a carbohydrate binder, the carbohydrate binder comprises component (a) in the form of one or more carbohydrates and component (b) in the form of (bi) one or more compounds selected from sulfamic acid, sulfamic acid derivatives or any salt thereof, wherein component (a) is present in an amount of at least 20% by weight based on the solids of the binder component. The aqueous binder composition is suitable for producing a mineral fiber product by contacting mineral fibers with the aqueous binder composition and curing the binder.

Description

TECHNICAL FIELD

[0001] The present invention relates to an aqueous binder composition comprising a mixture of a phenol-urea-formaldehyde binder and a carbohydrate binder; a method for producing a mineral wool product using the aqueous binder composition; and a mineral wool product prepared by the method. BACKGROUND

[0002] Mineral wool products typically comprise man-made vitreous fibres (MMVF), such as glass fibres, ceramic fibres, basalt fibres, slag wool, mineral wool and rock wool, which are bonded together by a cured thermoset polymeric binder material. In order to be used as thermal or acoustic insulation products, bonded mineral fibre mats are typically produced by converting a melt made from suitable raw materials into fibres in a conventional manner, for example by internal centrifugation (spinning cup process) or external centrifugation (cascade rotor process). The fibres are blown into a forming chamber or spinning chamber and sprayed with a binder solution while suspended and still hot, and the fibres are deposited randomly in the form of a mat or web onto a travelling conveyor belt. The fibre mat is then transferred to a curing oven in which heated air is blown through the mat to cure the binder and rigidly bond the mineral fibres together.

[0003] Phenolic binders, in particular phenol-formaldehyde resol, are often used in the manufacture of mineral fibre insulation materials, such as insulation wool for walls, roof boards, ceiling tiles, insulation coverings for pipes, etc.

[0004] Typically, when using phenol-formaldehyde resol as a binder, during processing, in particular in the spinning chamber where the binder is applied to the mineral fibres, and during curing, large amounts of formaldehyde are released into the environment. Formaldehyde can also be released subsequently from the cured resin. This formaldehyde emission is undesirable, especially in enclosed spaces, because it is harmful to human health and the environment. Formaldehyde has been classified as carcinogenic to humans by the International Agency for Research on Cancer (IARC) of the World Health Organization (WHO); see the IARC Monograph on Formaldehyde, Vol. 88 (2006). Therefore, it is desirable to reduce the release of formaldehyde into the environment.

[0005] Various techniques have been used to reduce the emission of formaldehyde from formaldehyde-based resins. In particular, various formaldehyde scavengers have been used to achieve this. For example, urea acts as a formaldehyde scavenger during the manufacture of bonded mineral fibre products and after the manufacture. Typically, urea is added directly to the phenol-formaldehyde resin to produce a urea-modified phenol-formaldehyde resol, also known as a phenol-urea-formaldehyde resol. In order to obtain a typical urea-modified resol binder resin, a mixture of phenol and formaldehyde is reacted in one or more steps with a suitable catalyst. The reaction conditions, temperature, amount of catalyst, etc. are adjusted to favour the methylation reaction of the phenol over the condensation reaction. Then, urea is added before or after the resin is deactivated before the resin is used. Such resins are typically referred to as PUF resins or PUF binders.

[0006] For example, US-A-4339361 discloses phenol-formaldehyde resols which are suitable for use in binder systems for bonded mineral fibre products and which are augmented with amides or amines such as urea and sugars as inexpensive augmenting agents. The sugar component can be selected from monosaccharides and oligosaccharides as well as water-soluble polysaccharides.

[0007] Modifying phenol-urea-formaldehyde binders with ammonia as a formaldehyde scavenger is also a known method to reduce the emission of formaldehyde from the binder during use. On the other hand, the modification with ammonia increases the ammonia emission of these systems. This is a particular problem when such binders are applied to mineral fibres in a spinning chamber. As mentioned above, when mineral fibres are produced, they are blown into such a spinning chamber and the mineral fibres are still hot. Under these conditions, the volatiles present in the binder which are not cured during the application will evaporate. As a result, when such binders are applied to mineral fibres in a spinning chamber, a relatively high ammonia emission is caused, which is highly undesirable. Again, this ammonia emission is also undesirable, especially in enclosed spaces, because it is harmful to human health and the environment.

[0008] Various techniques have been used to reduce the emission of both formaldehyde and ammonia from formaldehyde-based resins. In particular, sugar components have been used for this purpose, because the sugar will undergo a Maillard reaction with the ammonia in the phenol-formaldehyde resin during curing, thereby significantly inhibiting the ammonia emission.

[0009] For example, WO96 / 26164 describes a phenol-formaldehyde resin composition for use as a binder in mineral wool products, wherein the emission of phenol is reduced by using a stoichiometric excess of formaldehyde relative to the phenol, wherein the emission of excess formaldehyde is reduced by adding ammonia as a formaldehyde scavenger, and wherein the emission of ammonia is reduced by reacting the ammonia with a sugar compound. The sugar compound can be selected from monosaccharides, disaccharides and polysaccharides.

[0010] WO2012 / 076462 relates to a method of reducing formaldehyde emissions from mineral fibre products bonded with urea-modified phenol-formaldehyde resol-type adhesive, wherein dextrose is added to the uncured adhesive composition to act as a formaldehyde scavenger.

[0011] US2014 / 0113123 relates to a lignin-based adhesive comprising a lignosulfonate, a thermosetting resin selected from a phenol-formaldehyde resin or a urea-formaldehyde resin, a curing catalyst and an oligosaccharide as a filler. The lignosulfonate partially replaces the thermosetting resin, thereby reducing the content of free formaldehyde.

[0012] WO2016 / 10244A1 relates to an aqueous adhesive composition for mineral fibres comprising one or more components (i) in the form of a carbohydrate, one or more components (ii) in the form of a compound selected from aminosulfonic acid, a derivative of aminosulfonic acid or any salt thereof. The aqueous adhesive composition is a formaldehyde-free adhesive having formaldehyde product emissions below the following limit when tested according to the ISO 16000:2021 standard.

[0013] US-A-2010 / 0075146 relates to a sizing composition for mineral fibres intended to reduce undesirable emissions, comprising a phenol-urea-formaldehyde resin and a catalyst made from a mixture of ammonium aminosulfonate and ammonium sulfate. The sizing composition is augmented with sugar as an inexpensive extender. The sugar component can be sugar cane or sugar beet molasses.

[0014] Such phenol-formaldehyde resol-based adhesives, which use a formaldehyde scavenger such as urea or ammonia and use sugar as an ammonia scavenger, show advantageous lower formaldehyde emissions and ammonia emissions compared to conventional phenol-formaldehyde adhesives. However, compared to the known conventional phenol-formaldehyde adhesives described above, they still have some disadvantages in terms of higher curing temperatures and mechanical properties at most equal or lower than conventional phenol-formaldehyde adhesives. Phenol-formaldehyde adhesives with carbohydrates can show higher solubility and higher water absorption in their cured state, which are undesirable properties as this impairs their use in certain application fields.

[0015] Therefore, there is still a need to provide aqueous adhesive compositions based on phenol-formaldehyde-type adhesives, which are suitable for bonding mineral fibres to produce mineral fibre products, wherein the adhesive composition produces only small amounts of harmful gases during processing. In particular, the ammonia, formaldehyde and phenol emissions should be reduced and kept low. At the same time, the mineral fibre products resulting from the application of the adhesive to the mineral fibres and curing should have very good long-term mechanical properties and a satisfactory low water absorption (or water uptake) and low solubility. SUMMARY

[0016] It is therefore an object of the present invention to provide an aqueous binder composition suitable for bonding mineral fibres, which overcomes or mitigates the above-mentioned drawbacks of the prior art.

[0017] In particular, it is an object of the present invention to provide a phenol-urea-formaldehyde based binder for mineral fibres, which has reduced ammonia emissions during processing of the binder, while formaldehyde and phenol emissions remain low, in particular during application of the binder to the mineral fibres in the spinning chamber, where the temperature of the fibres is still high. At the same time, the binder in the cured state should show satisfactory properties in terms of mechanical strength, solubility and water absorption.

[0018] The inventors have surprisingly found that this object can be solved by providing a binder composition made from a mixture of a phenol-urea-formaldehyde type binder (PUF binder) and a specific carbohydrate binder.

[0019] According to a first aspect of the present invention, there is provided an aqueous binder composition, in particular for mineral fibres, made from a mixture of:

[0020] I) a phenol-urea-formaldehyde binder (PUF binder), and

[0021] II) a carbohydrate binder, comprising:

[0022] component (a) in the form of one or more carbohydrates;

[0023] component (b) in the form of:

[0024] (bi) one or more compounds selected from aminosulfonic acid, aminosulfonic acid derivatives or any salts thereof,

[0025] wherein component (a) is present in an amount of at least 20 wt.%, based on binder component solids.

[0026] The inventors have surprisingly found that the mixed binder described herein provides improved mechanical properties compared to both pure PUF binders and pure carbohydrate binders.

[0027] In particular, the addition of the specific carbohydrate binder to the PUF binder not only reduces ammonia emissions during processing, but also reduces formaldehyde and phenol emissions, in particular during application of the binder to the mineral fibres in the spinning chamber.

[0028] In a PUF binder modified with ammonia as formaldehyde scavenger, the addition of the carbohydrate binder not only leads to a significant reduction in ammonia emissions, but also significantly reduces formaldehyde and phenol emissions. Typically, the reduction in ammonia emissions is proportional to the replacement of water, while the reduction in formaldehyde and phenol emissions is even more pronounced.

[0029] PUF adhesives that do not contain ammonia as a formaldehyde scavenger remove most ammonia emissions, but also result in very high formaldehyde emissions. These formaldehyde emissions from ammonia-free PUF adhesives can then be significantly reduced by partially replacing them with carbohydrate-based adhesives.

[0030] As a result, the inventive mixture of PUF adhesive (component (I)) and carbohydrate adhesive (component (II)) reduces ammonia, formaldehyde, and phenol emissions compared to pure PUF adhesive. This opens the possibility of partially or completely removing ammonia from the aqueous adhesive compositions described herein.

[0031] Compared to pure PUF, the inventive blended adhesives generally maintain or are at a comparable level of mechanical strength, and in most cases even significantly improve mechanical strength compared to pure carbohydrate adhesives. In particular, the aged mechanical strength is typically significantly improved compared to both pure PUF adhesives and carbohydrate adhesives.

[0032] When starting with carbohydrate binders, the addition of PUF binder also leads to significant improvements compared to pure carbohydrate binders. As mentioned above, a disadvantage of pure carbohydrate binders is their relatively high water absorption in the cured state. However, even mixing a small amount of PUF binder into a carbohydrate binder results in a reduction in the water absorption of the insoluble binder after curing. Without being limited by theory, this suggests that PUF binder is highly effective as a crosslinking agent for carbohydrate binders.

[0033] The improvements described for hybrid adhesives are so significant that they cannot usually be explained by additive effects, but rather demonstrate a synergistic interaction between the two adhesive systems being blended.

[0034] Further advantages and features of the invention will become apparent from the description of the preferred embodiments and the accompanying drawings, which illustrate:

[0035] Figure 1 shows a comparison of the mechanical strength of unaged and aged composite rods of the present invention and prior art, wherein composite rods bonded by pure PUF adhesive are depicted as (A), composite rods bonded by three different adhesive mixtures as described herein are depicted as Examples 1-3, composite rods bonded by pure carbohydrate adhesive are depicted as (C2), composite rods bonded by prior art carbohydrate adhesives (D1-D3), and composite rods bonded by glucose alone are depicted as (B).

[0036] Figure 2 shows a comparison of simulated spinning chamber emissions for pure PUF adhesive (A), carbohydrate adhesives in three different adhesive mixtures as described herein (Examples 1–3), and pure carbohydrate adhesive (C2). Detailed Implementation

[0037] This invention relates to an aqueous adhesive composition for mineral fibers, the aqueous adhesive composition being made from a mixture of the following substances:

[0038] I) Phenol-urea-formaldehyde adhesive (PUF adhesive), and

[0039] II) Carbohydrate binders, comprising:

[0040] Component (a) is in the form of one or more carbohydrates;

[0041] Component (b) is in the following form:

[0042] (bi) One or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof.

[0043] Component (a) is present in an amount of at least 20% by weight based on the solids content of the adhesive component.

[0044] The aqueous adhesive composition of the present invention is a mixed adhesive composition obtainable by mixing two separate adhesives, namely a phenol-urea-formaldehyde adhesive and a carbohydrate adhesive. Here, the phenol-urea-formaldehyde adhesive is also called a PUF adhesive, which is a common name for such an adhesive system. The separate adhesives are usually complete adhesives that can be used as adhesives.

[0045] In a preferred embodiment, the aqueous adhesive composition of the present invention is a mixed adhesive composition that can be obtained by online mixing of the following substances:

[0046] -Independent phenol-urea-formaldehyde adhesive (PUF),

[0047] - Component (a), which is in the form of one or more carbohydrates,

[0048] - Component (b), which is in the following form:

[0049] (bi) One or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof.

[0050] -Optional component (bii), which is in the form of one or more compounds selected from hypophosphite, hypophosphite derivatives or any salt thereof,

[0051] -Optional ammonia,

[0052] -Optional urea,

[0053] -Optional silane,

[0054] -water.

[0055] In a preferred alternative embodiment, the aqueous adhesive composition of the present invention is a mixed adhesive composition that can be obtained by online mixing of the following substances:

[0056] -Phenol-urea-formaldehyde resin,

[0057] -ammonia,

[0058] -Ammonium sulfate,

[0059] - Component (a), which is in the form of one or more carbohydrates,

[0060] - Component (b), which is in the following form:

[0061] (bi) One or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof.

[0062] -Optional component (bii), which is in the form of one or more compounds selected from hypophosphite, hypophosphite derivatives or any salt thereof,

[0063] -Optional urea,

[0064] -Optional silane,

[0065] -water.

[0066] Online mixing is preferably performed using a static mixer. Alternatively, online mixing can be performed via a stationary device, whereby the mixture must flow through the stationary device to be mixed.

[0067] The aqueous adhesive composition of the present invention, as well as the PUF adhesive and the carbohydrate adhesive, are particularly suitable as adhesives for mineral fibers in the production of mineral fiber products.

[0068] The adhesive composition of the present invention is an aqueous adhesive composition, meaning that the adhesive composition contains water. Typically, both PUF adhesives and carbohydrate adhesives are aqueous adhesives. Water may be added to the mixture if necessary, for example, to adjust desired properties (such as viscosity).

[0069] Component (I) - PUF binder

[0070] Phenol-urea-formaldehyde adhesives (PUF adhesives) based on phenol-urea-formaldehyde resin (PUF resin) are known to those skilled in the art and have a wide range of applications, such as as adhesives for mineral fibers in the production of mineral fiber products.

[0071] According to the present invention, the properties of the PUF adhesive are not critical, and any PUF adhesive known in the art can be used. A PUF adhesive that is a mixture of phenolic adhesive (PF adhesive) and urea-formaldehyde adhesive (UF adhesive) can also be used.

[0072] The starting materials used to prepare PUF-based PUF adhesives are typically phenol, urea, formaldehyde, and a base as a catalyst. Optionally, additional materials may be used in the reaction, such as formaldehyde scavengers like ammonia, and curing agents such as ammonium salts like ammonium sulfate. Formaldehyde may be introduced into the reaction, for example, as an aqueous solution (formalin) or in the form of p-formaldehyde.

[0073] The base used in the preparation of PUF resins or adhesives may include at least one basic alkali metal or alkaline earth metal compound or amine catalyst, such as triethylamine (TEA). Examples of usable alkali metal bases include hydroxides of sodium, potassium, and lithium. Examples of usable alkaline earth metal bases include oxides and hydroxides of calcium, barium, and strontium, such as calcium oxide and calcium hydroxide.

[0074] The PUF adhesives used in the aqueous adhesive compositions described herein are typically phenol-urea-formaldehyde methylphenolic resin adhesives. Methylphenolic resins or methylphenolic resin-type adhesives are obtained by using an excess of formaldehyde relative to the stoichiometry of phenol (i.e., a molar ratio of aldehyde to phenol greater than 1).

[0075] Specific examples of suitable PUF methyl phenolic resins or adhesives include those disclosed in EP-A-148050, EP-A-810981, CA-A-1001788 and US-A-5371140; emulsifiable phenolic resins disclosed in EP-A-1084167; and over-condensed phenolic resins disclosed in WO 99 / 03906 and WO 2009 / 136106.

[0076] The production of PUF adhesives or PUF resins typically involves reacting phenol and formaldehyde in an aqueous alkaline solution to prepare phenolic resins. Urea may be introduced during or after resin preparation to obtain phenol-urea-formaldehyde resins.

[0077] In a preferred embodiment, the molar ratio of phenol to formaldehyde used to prepare the PUF adhesive is 1:2.5 to 1:6, preferably 1:3 to 1:5.

[0078] In a preferred embodiment, the amount of urea used to prepare the PUF adhesive is 20 to 60% by weight, preferably 30 to 50% by weight, based on the total weight of phenol, formaldehyde and urea used to prepare the PUF adhesive.

[0079] More specifically, an exothermic condensation reaction of phenol and aldehyde is initiated after mixing phenol and aldehyde by adding an aqueous base. For example, with the addition of an alkaline catalyst, the aqueous mixture of phenol and formaldehyde can be maintained at a first temperature, for example, 40 to 50°C. The temperature can then be raised to a second reaction temperature, for example, 60 to 90°C. In an alternative embodiment, the aqueous mixture of phenol and formaldehyde can be heated to a final temperature, for example, 60 to 90°C (for example, about 84°C), at a continuous heating rate (e.g., 0.5°C / min to 1.5°C / min, such as about 1°C / min) in the presence of an alkaline, and held at that final temperature for a certain period of time.

[0080] Preferably, the reaction of phenol and formaldehyde is carried out at a suitable temperature for a sufficient duration to provide an acid resistance of <8, preferably in the range of 0.5 to 7, more preferably 3 to 5, and most preferably a methylphenolic resin. Acid resistance is a measure of the degree of reaction. The method for its determination is given in the experimental section below.

[0081] The conversion rate of phenol is preferably >95%, more preferably >97%.

[0082] Urea, particularly methylphenolic resins, can be added to the resin during resin preparation or in post-reaction steps.

[0083] The PUF resin or PUF adhesive may be an ammonia-modified PUF resin or PUF adhesive. Alternatively, the PUF resin or PUF adhesive may be an unmodified PUF resin or PUF adhesive.

[0084] As described, ammonia can act as a formaldehyde scavenger. Preferably, PUF adhesives are modified with ammonia. Modification of PUF resins or PUF adhesives with ammonia is carried out by adding ammonia (e.g., as a gas but usually in the form of an aqueous solution of ammonia) to the reactive material or PUF resin, preferably after the formation of a phenol-urea-formaldehyde resin or a phenol-urea-formaldehyde methylformaldehyde resin. It should be noted that here, ammonia refers only to ammonia itself, i.e., it does not include ammonium salts that can be added as additives. This also applies to the following instructions regarding suitable amounts.

[0085] In a preferred embodiment, the amount of ammonia is 0 to 6% by weight, more preferably 0 to 4% by weight, and even more preferably 0 to 3% by weight, based on the solids of the adhesive component of the PUF adhesive.

[0086] As described above, PUF adhesives are more preferably modified with ammonia, and in this case, a suitable lower limit for ammonia may be, for example, at least 0.1% by weight based on the solids content of the adhesive component of the PUF adhesive. Therefore, in the case of ammonia modification, the amount of ammonia may be, for example, 0.1 to 6% by weight based on the solids content of the adhesive component of the PUF adhesive, preferably 0.5 to 4% by weight, more preferably 1 to 3% by weight. The solids content of the adhesive component of the PUF adhesive is defined in the following description of the mixture.

[0087] The resulting aqueous composition containing PUF resin (preferably PUF methyl phenolic resin) can be used as a PUF adhesive for the aqueous adhesive composition of the present invention. Optionally, water can be added to adjust the viscosity of the PUF adhesive.

[0088] In addition, additives may optionally be added to the PUF adhesive. Hardeners such as ammonium sulfate or acids such as sulfuric acid may be added to the reaction mixture.

[0089] Component (II) - carbohydrate binder

[0090] The second adhesive component of the aqueous adhesive composition described herein is a carbohydrate adhesive, which comprises:

[0091] - Component (a), which is in the form of one or more carbohydrates, and

[0092] - Component (b), which is in the following form:

[0093] (bi) One or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives or any salt thereof.

[0094] Carbohydrate adhesives are typically water-based. These adhesives may contain one or more carbohydrates. Furthermore, carbohydrate adhesives are formaldehyde-free because no formaldehyde is added.

[0095] For the purposes of this application, the term "formaldehyde-free" is also defined as characterizing mineral wool products with curing adhesives, wherein formaldehyde emissions from the mineral wool products are less than 5 μg / m³. 2 / h, preferably below 3 μg / m 2 / h. Preferably, the aldehyde emissions are tested according to ISO 16000:2021.

[0096] Component (a) of the binder

[0097] Component (a) is in the form of one or more carbohydrates.

[0098] Starch can be used as a raw material for various carbohydrates such as glucose syrups and glucose. Depending on the reaction conditions used in the hydrolysis of starch, various mixtures of glucose and intermediates are obtained, which can be characterized by their DE values. DE is an abbreviation for Dextrose Equivalent and is defined as the content of reducing sugars, determined by the method specified in the international standard ISO 5377-1981 I. This method measures the reducing end groups, setting the DE of pure glucose at 100 and the DE of pure starch at 0.

[0099] In a preferred embodiment, the carbohydrate is selected from sucrose, reducing sugars, particularly glucose, polysaccharides, and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, and even more preferably glucose syrups with a glucose equivalent value DE = 30 to 100, such as DE = 50 to 100, such as DE = 60 to 100, such as DE = 85 to 100, such as DE = 95 to 100. As used herein, the term "glucose" is defined to include glucose and its hydrates, such as D-glucose.

[0100] In a preferred embodiment, the carbohydrate has a DE value of 60 to 100, particularly 85 to 100, and even more particularly 95 to 100.

[0101] In a preferred embodiment, the carbohydrate is glucose having a DE value of 85 to 100.

[0102] In another preferred embodiment, the carbohydrate is selected from pentoses, particularly allose, arbutin, glucose, mannose, gulose, idulose, galactose, tarose, allulose, fructose, sorbose and / or tagatose; and / or pentoses, particularly arabinose, lysose, ribose, xylose, ribulose and / or xylulose; and / or tetrasaccharides, particularly erythrose, threose and / or erythulose.

[0103] In another preferred embodiment, the carbohydrate is selected from sugars such as fructose, and / or pentoses such as xylose.

[0104] The carbohydrate binder component (a) is present in an amount of at least 20% by weight based on the solids content of the binder component. In a preferred embodiment, component (a) is present in an amount of 20 to 90% by weight of the solids content of the binder component, more preferably in an amount of 40 to 90% by weight of the solids content of the binder component, and most preferably in an amount of 60 to 80% by weight of the solids content of the binder component.

[0105] Since the carbohydrates in component (a) are relatively inexpensive compounds and are produced from renewable materials, including a large amount of component (a) in carbohydrate adhesives allows for the production of adhesives in an ecologically and economically advantageous manner.

[0106] Component (b) of the binder

[0107] Component (b) of the adhesive is in the following form:

[0108] (bi) one or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives or any salt thereof, and alternatively

[0109] (bii) One or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof.

[0110] In a preferred embodiment, the proportion of component (b) of the aqueous carbohydrate adhesive composition is in the range of 1 to 15% by weight, particularly 1 to 12% by weight, and more particularly 2 to 10% by weight, based on the solid content of the adhesive component.

[0111] Component (bi) of component (b)

[0112] In one embodiment of the invention, component (bi) is in the form of one or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salts thereof. Aminosulfonic acids are non-toxic compounds having the following formula:

[0113] .

[0114] Sulfoamic acid and its many salts are storage-stable, non-volatile compounds and are available at relatively low cost. In a preferred embodiment, component (bi) is selected from sulfamic acid and any salt thereof, such as ammonium sulfamic acid, calcium sulfamic acid, sodium sulfamic acid, potassium sulfamic acid, magnesium sulfamic acid, cobalt sulfamic acid, nickel sulfamic acid, N-cyclohexylsulfamic acid and any salt thereof, such as sodium N-cyclohexylsulfamic acid.

[0115] In a preferred embodiment, the proportion of component (bi) of the aqueous carbohydrate adhesive composition, based on the solids content of the adhesive component, is in the range of 0.5-20% by weight, particularly 1-15% by weight, more particularly 1-10% by weight, such as 2-10% by weight, and most particularly 1-5% by weight.

[0116] In a preferred embodiment, component (bi) is aminosulfonic acid.

[0117] In a particularly preferred embodiment, component (bi) is ammonium aminosulfonate.

[0118] In another preferred embodiment, component (bi) is in the form of N-cyclohexylsulfamic acid and any salt thereof. Based on the mass of the solids content of the binder component, the proportion of component (bi) in the form of N-cyclohexylsulfamic acid and any salt thereof is in the range of 0.5-20% by weight, particularly 1-15% by weight, more particularly 1-10% by weight, such as 2-10% by weight, and most particularly 1-5% by weight.

[0119] The advantage of the binder component (bi) is that it helps reduce curing temperature and reaction loss during curing. Lower reaction loss results in lower emissions. Furthermore, it is relatively inexpensive and easy to handle.

[0120] Component (bii) of component (b)

[0121] In an embodiment of the invention, component (b) of the carbohydrate binder further comprises component (bii), which is in the form of one or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof.

[0122] Hypophosphorous acid, H3PO2 (or H2PO(OH)), is an inorganic acid with the following formula.

[0123] .

[0124] In a preferred embodiment, the component (bii) is hypophosphorous acid.

[0125] In another preferred embodiment, the component (bii) is ammonium hypophosphite or sodium hypophosphite.

[0126] In a preferred embodiment, component (b) is a mixture of components (bi) and (bii), namely, a mixture of aminosulfonic acid, aminosulfonic acid derivatives or any salt thereof with hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof.

[0127] In a preferred embodiment, the proportion of the component (bii) of the aqueous carbohydrate adhesive composition (adhesive component solids) is in the range of 0.25 to 10% by weight, particularly 0.5 to 7.5% by weight, and more particularly 0.5 to 5% by weight, based on the solids content of the adhesive component.

[0128] Surprisingly, it has been shown that adding inorganic acids, such as hypophosphite, to aqueous binder compositions can greatly improve the mechanical properties of aqueous carbohydrate compositions.

[0129] Component (bii) can be used as a single component in component (b) of the carbohydrate adhesive portion of the inventive aqueous adhesive composition. However, a disadvantage of using only component (bii) in the carbohydrate adhesive portion of the aqueous adhesive composition as described herein is its relatively high price.

[0130] The inventors have discovered that by including component (b) as a mixture of component (bi) and component (bii) in the aqueous adhesive composition, the unaged and aged mechanical strength of the aqueous adhesive composition described herein can be greatly improved.

[0131] In another preferred embodiment, the ratio of component (bi) to component (bii) in the aqueous adhesive composition is ≥1:1, more preferably 3:1 to 5:1, and most preferably 4:1.

[0132] In particular, the inventors have discovered that adding component (bii), namely hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof, at a ratio of 4:1 to component (bii) in the aqueous adhesive composition according to the invention almost doubles the mechanical strength under aging compared to including only component (bi), namely aminosulfonic acid, aminosulfonic acid derivatives or any salt thereof, in the aqueous adhesive composition according to the invention.

[0133] Furthermore, compared to adding only component (bi), by including a mixture of component (bi) and component (bii) in the water-based adhesive, the curing start temperature and curing end temperature of the water-based adhesive of the present invention can be reduced.

[0134] In a preferred embodiment, the carbohydrate binder composition further comprises a component (c) in the form of ammonia. The amount of ammonia is preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight, based on the solids content of the binder component.

[0135] In an alternative embodiment, component (c) is preferably in the form of an ammonium salt.

[0136] Without being bound by any theory, it is believed that the strong cross-linking of ammonia with the aldehyde groups of carbohydrates leads to a reduction in both ammonia and formaldehyde emissions when the inventive mixture of PUF adhesive and carbohydrate adhesive is used compared to pure PUF adhesive.

[0137] In another preferred embodiment, the aqueous carbohydrate adhesive composition further comprises a component (d) in the form of urea. The amount of urea is preferably 0.5 to 6% by weight, more preferably 1 to 5% by weight, and most preferably 2 to 4% by weight, based on the weight of the solids of the adhesive component.

[0138] The inclusion of urea in the adhesives described herein improves the fire resistance and anti-punking properties of the inventive adhesives.

[0139] Final binder composition - mixing of component (I) and component (II)

[0140] According to the present invention, the carbohydrate binder composition for mineral fibers is based on a combination of: a carbohydrate component (a); and a component (b) selected from one or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salts thereof, and optionally one or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives, or any salts thereof, or any mixture thereof. Surprisingly, a binder composition suitable for bonding mineral fibers can be prepared by combining these two components (a) and (b). Both components are relatively inexpensive and easy to handle.

[0141] The aqueous adhesive composition of the present invention can be obtained, for example, by adding a carbohydrate adhesive (component (II)) to a phenol-urea-formaldehyde adhesive (component (I)) or vice versa, and mixing the resulting mixture using a mixing device if necessary. Common mixing devices, such as mixing tanks or static mixers, can be used.

[0142] To obtain the aqueous adhesive composition of the present invention, it is preferred that the PUF adhesive and the carbohydrate adhesive are mixed in a certain ratio such that the weight proportion of B based on the combined weight of A+B is in the range of 20 to 95% by weight, more preferably 25 to 95% by weight, wherein B is the weight of the adhesive solids of the carbohydrate adhesive (component II) and A is the weight of the adhesive solids of the PUF adhesive (component (I)).

[0143] More preferably, based on the combined weight of A+B, the weight proportion of B may, for example, be appropriately in the range of 25 to 90% by weight of the adhesive solids.

[0144] This invention can also be used to improve the properties of PUF adhesives or carbohydrate adhesives, depending on whether the PUF adhesive or carbohydrate adhesive is a major component of the aqueous adhesive composition of this invention.

[0145] Therefore, when the PUF adhesive is the main component of the aqueous adhesive composition of the present invention, based on the combined weight of A+B, the weight ratio of B is preferably in the range of 5 to 50% by weight of the adhesive solids, more preferably 10 to 45% by weight, or even more preferably 15 to 40% by weight, 20 to 40% by weight, or 25 to 40% by weight.

[0146] As can be seen from the experimental section below and Figure 2, even incorporating a low proportion of carbohydrate binder (component (II)) into the PUF binder (component (I)) resulted in a significant reduction in ammonia emissions, and particularly in the ammonia-modified PUF binder, a significant reduction in formaldehyde and phenol emissions was achieved. A significant reduction in formaldehyde emissions was also obtained in the unmodified PUF binder compared to the pure binder.

[0147] When the carbohydrate binder is the main component of the aqueous adhesive composition of the present invention, the weight percentage of B, based on the combined weight of A and B, is preferably in the range of 50 to 95% by weight, more preferably 55 to 90% by weight, and even more preferably 60 to 80% by weight. In other words, the weight percentage of A, based on the combined weight of A and B, is preferably in the range of 5 to 50% by weight, more preferably 10 to 45% by weight, and most preferably 20 to 40% by weight.

[0148] As can be seen from the experimental section below, even mixing a low proportion of PUF adhesive into the carbohydrate adhesive results in a lower water absorption rate of the resulting adhesive compared to the carbohydrate adhesive itself.

[0149] Furthermore, compared to both pure PUF adhesives and pure carbohydrate adhesives, the inventive aqueous adhesive composition described herein results in very good mechanical strength for mineral fiber products produced using the inventive adhesive. As can be seen from Figure 1, the unaged (top two curves), and aged (bottom two curves) mechanical strengths of the mineral fiber products produced using the inventive adhesive (described as Example 1 (25:75), Example 2 (50:50), and Example 3 (75:25)) are generally higher than those of the prior art carbohydrate adhesives (described as D1-D3) and pure glucose (described as (B)). Although the experimental section and Figure 1 show a slight decrease in unaged mechanical strength compared to pure PUF adhesive (described as (A)), the aged mechanical strength is significantly improved overall.

[0150] The adhesive described herein may have any pH. Preferably, the adhesive has a pH of 6-11, more preferably 7-11. In a particularly preferred embodiment, the adhesive has a pH of 7-10.

[0151] Therefore, the adhesive of the present invention is not strongly acidic, and therefore not strongly corrosive.

[0152] In the context of this invention, "adhesive component solids" and "adhesive solids" are defined as follows.

[0153] Binder component solids content - definition

[0154] The weight content of each component in a given adhesive solution prior to curing is based on the anhydrous mass of the component, i.e., excluding solvents, particularly water. The following formula can be used:

[0155] If only the solids content of the binder component is calculated, then binder component A will be glucose.

[0156] In calculating the solid content of the binder component in any given binder containing carbohydrates, A could be, for example, glucose and B could be, for example, fructose.

[0157] In the case of PUF adhesives, formaldehyde and (if used) ammonia are also considered components of the adhesive. Although these starting materials are volatile, they react at least partially during the preparation of the PUF resin.

[0158] Binder solids - definition and procedure

[0159] The weight percentage of the adhesive after curing is called the "adhesive solids content".

[0160] Disc-shaped asbestos samples (5 cm in diameter and 1 cm in height) were cut from the asbestos and heat-treated at 590°C for at least 30 minutes to remove all organic matter. The solids content of the adhesive was measured by dispensing a sample of the adhesive (approximately 2 g) onto the heat-treated asbestos discs in a foil container. The foil containers containing the asbestos discs were weighed immediately before and after the addition of the adhesive. Two such adhesive-loaded asbestos discs were produced in foil containers and then heated at 200°C for 1 hour. After cooling at room temperature and storing for 10 minutes, the samples were weighed, and the adhesive solids content was calculated by averaging the two results and then expressed as a percentage by weight.

[0161] Reaction loss - definition

[0162] Reaction loss is defined as the difference between the solid content of the binder component and the solid content of the binder.

[0163] Additives

[0164] The aqueous adhesive composition of the present invention may further include one or more additives.

[0165] The aqueous adhesive composition of the present invention may contain one or more additives selected from the group consisting of mineral oils, organosilicones and / or silanes.

[0166] Preferably, one or more additives may contain silanes, one or more hydrophobic agents such as organosilicon and / or one or more mineral oils.

[0167] These additives may be hydrophobic components, such as one or more reactive or non-reactive organosilicon compounds, and may be added to the adhesive composition. Preferably, the one or more reactive or non-reactive organosilicon compounds are selected from: organosilicon compounds consisting of a backbone composed of organosiloxane residues, particularly diphenylsiloxane residues, alkylsiloxane residues, preferably dimethylsiloxane residues, having at least one hydroxyl, carboxyl or anhydride, amine, epoxy or vinyl functional group capable of reacting with at least one component of the adhesive composition, and preferably present in an amount of 0.1-15% by weight, preferably 0.1-10% by weight, more preferably 0.3-8% by weight based on the adhesive solids.

[0168] If producing hydrophilic mineral wool products, such as horticultural growing media, mineral wool products for permeability and water buffering, or shock-absorbing pads for sports fields, arenas, or playgrounds, the addition of silicone can be omitted.

[0169] The hardener, such as a silane, is preferably present in an amount of 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, and more preferably 0.1 to 0.8% by weight, based on the binder solids. Preferably, one or more silanes are amino-functionalized silanes, such as Dynasylan from Evonik Industries. ® HYDROSIL 1151. As described above, one or more mineral oils can be added to an aqueous adhesive composition.

[0170] Additives can be added before or after mixing the final adhesive.

[0171] Method of producing a mineral fibre product

[0172] The present invention also relates to a method for producing adhesive mineral fiber products, the method comprising the steps of contacting the mineral fibers with the aqueous adhesive composition described herein and curing the adhesive.

[0173] The aqueous adhesive compositions have been described above. Of course, all the instructions discussed above regarding the aqueous adhesive compositions also apply to the aqueous adhesive compositions used in the methods of the present invention.

[0174] The mineral fibers used can be, for example, any man-made glass fiber (MMVF), glass fiber or glass wool, ceramic fiber, basalt fiber, slag fiber, stone fiber or asbestos, etc. The mineral fibers are preferably of the type commonly referred to as rock fiber, stone fiber or slag fiber, with stone fiber being the most preferred. These fibers can exist as cotton products, such as asbestos products.

[0175] Artificial glass fibers can have any suitable oxide composition.

[0176] In the following text, iron oxide may be a mixture of FeO and Fe2O3, but is referred to as Fe2O3 in this document.

[0177] Stone fibers typically contain the following oxides, by weight percentage:

[0178] SiO2: 30 to 51

[0179] Al2O3: 12 to 25

[0180] CaO: 8 to 30

[0181] MgO: 2 to 25

[0182] Fe2O3: 2 to 15

[0183] Na₂O + K₂O: not exceeding 10

[0184] CaO+MgO: 10 to 30

[0185] In a preferred embodiment, the artificial glass fiber has the following elemental levels, calculated as a percentage by weight of oxides:

[0186] SiO2: at least 30, 32, 35 or 37; not exceeding 51, 48, 45 or 43

[0187] Al2O3: at least 12, 16, or 17; not exceeding 30, 27, or 25

[0188] CaO: at least 8 or 10; not exceeding 30, 25 or 20

[0189] MgO: at least 2 or 5; not more than 25, 20 or 15

[0190] FeO (including Fe2O3): at least 4 or 5; not exceeding 15, 12 or 10

[0191] FeO+MgO: at least 10, 12 or 15; not exceeding 30, 25 or 20

[0192] Na₂O + K₂O: zero or at least 1; not exceeding 10

[0193] CaO + MgO: at least 10 or 15; not exceeding 30 or 25

[0194] TiO2: zero or at least 1; not exceeding 6, 4 or 2

[0195] TiO2+FeO: at least 4 or 6; not exceeding 18 or 12

[0196] B2O3: zero or at least 1; not exceeding 5 or 3

[0197] P2O5: zero or at least 1; not exceeding 8 or 5

[0198] Other: zero or at least 1; not exceeding 8 or 5

[0199] Glass fibers typically contain the following oxides, in weight percentage:

[0200] SiO2 50 to 70

[0201] Al2O3 10 to 30

[0202] CaO not exceeding 27

[0203] MgO not exceeding 12

[0204] Glass fibers may also contain the following oxides, by weight percentage:

[0205] The inequality of Na₂O + K₂O is 8 to 18, especially Na₂O + K₂O is greater than that of CaO + MgO, and

[0206] B2O33 to 12.

[0207] Some glass fiber compositions may contain less than 2% Al2O3.

[0208] Artificial glass fibers can be prepared from mineral melts. The mineral melt is provided in a conventional manner by supplying mineral materials and melting them in a furnace. This furnace can be any type of furnace known for producing mineral melts of artificial glass fibers, such as shaft furnaces, cupola furnaces, tank furnaces, submerged electric furnaces, or cyclone furnaces.

[0209] Artificial glassy fibers can be formed from mineral melts by any suitable method. Fiberization can be achieved via a rotary cup process, in which the melt is centrifugally extruded through orifices in the wall of a rotating cup (rotary cup, also known as internal centrifugation). Alternatively, fiberization can be achieved by centrifugal fiberization by spraying the melt onto the outer surface of a single fiberizing rotor and spinning it from there; or by spraying the melt onto the outer surfaces of multiple cascaded fiberizing rotors rotating about a substantially horizontal axis (cascade spinning machine).

[0210] Therefore, the melt forms a cloud of fibers entrained in the air, and the fibers are collected as a web on a conveyor belt and transported away from the fiberizing device. The fiber web is then consolidated, which may include cross-laying and / or longitudinal compression and / or vertical compression and / or winding around a mandrel to produce a cylindrical product for pipe insulation. Other consolidation processes may also be performed.

[0211] The step of bringing the mineral fibers into contact with the water-based adhesive composition can be achieved by applying the water-based adhesive composition to the mineral fibers using conventional means such as spraying.

[0212] The adhesive composition is preferably applied to the fibers when they are clouds entrained in the air. Alternatively, the adhesive composition may be applied after the fibers have been collected on a conveyor belt, but this is less preferred.

[0213] After consolidation, the consolidated fiber web is fed into a curing device to cure the adhesive.

[0214] The curing process can begin immediately after the adhesive is applied to the fibers. Curing is defined as the process by which the adhesive composition undergoes a physical and / or chemical reaction, wherein, in the case of a chemical reaction, the molecular weight of the compounds in the adhesive composition typically increases and thereby increases the viscosity of the adhesive composition, typically until the adhesive composition reaches a solid state. The cured adhesive composition bonds the fibers to form a structurally coherent fibrous matrix.

[0215] In one embodiment, the curing process includes pressure drying. Pressure can be applied by blowing air or gas through / through a mixture of mineral fibers and adhesive.

[0216] In one embodiment, the curing process includes a drying process. In another embodiment, the curing process includes pressure drying. Pressure can be applied by blowing air or gas into the mixture of mineral fibers and adhesive. The blowing process may be accompanied by heating or cooling, or it may be carried out at ambient temperature.

[0217] In one implementation, curing is carried out in curing equipment such as a conventional curing oven or a hot press.

[0218] The curing of adhesive compositions that come into contact with mineral fibers in a hot press has a particular advantage: it enables the production of high-density products.

[0219] The curing of the aqueous adhesive composition in contact with mineral fibers can be carried out over a wide temperature range. In one embodiment, curing is carried out at a temperature of 180 to 360°C, preferably at a temperature of 200 to 275°C, and more preferably at a temperature of 220 to 250°C.

[0220] In one implementation, curing takes 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.

[0221] In a typical implementation, curing is carried out at a temperature of 150 to 250°C for 30 seconds to 20 minutes.

[0222] Another advantage of the adhesives described in this article is that they have a relatively high curing speed at low curing temperatures.

[0223] Compared to previously known carbohydrate adhesives, the adhesive described herein offers a higher curing speed, allowing for increased production capacity in plants manufacturing bonded mineral fiber products. Simultaneously, the lower curing temperature required by the adhesive described herein, compared to carbohydrate adhesives, saves energy during production and limits the emission of volatile compounds.

[0224] In a preferred embodiment, an aqueous binder composition is applied near the fiber forming apparatus, such as a cascade spinning apparatus or a cup spinning apparatus, in any case immediately after fiber formation. Therefore, it is preferable to apply the aqueous binder composition to the mineral fibers formed in the spinning chamber, preferably by spraying. Thereafter, the binder-coated fibers are typically conveyed as a web, such as a collection web, onto a conveyor belt. The web, such as the collection web, may undergo longitudinal or length compression after fiber formation and before substantial curing occurs.

[0225] In a preferred embodiment, the method for producing the adhesive mineral fiber product includes the following steps:

[0226] -The melt used to manufacture raw materials,

[0227] - The melt is fiberized by a fiber forming device to form mineral fibers, wherein the formed mineral fibers are preferably guided into a spinning chamber.

[0228] - Provides mineral fibers in the form of a collection net.

[0229] - An aqueous binder composition is applied to the mineral fibers before, during, or after the collection net is provided to form a mixture of the mineral fibers and the binder composition, wherein the aqueous binder composition is preferably applied by spraying before the collection net is provided, preferably in the spinning chamber.

[0230] - To cure the adhesive composition mixed with mineral fibers.

[0231] Various types of centrifugal spinning machines exist, which are used as fiber forming devices to fiberize mineral melts.

[0232] A conventional centrifugal spinning machine is a cascade spinning machine, which comprises a series of top (or first) rotors and subsequent (or second) rotors, as well as optional other subsequent rotors (such as third and fourth rotors). Each rotor rotates about a different, substantially horizontal axis, wherein the direction of rotation is opposite to the direction of rotation of each adjacent rotor in the sequence. The different horizontal axes are arranged such that the melt poured onto the top rotor is successively thrown onto the peripheral surface of the subsequent rotors or each subsequent rotor, and fibers are ejected from the subsequent rotors or each subsequent rotor, and optionally also from the top rotor.

[0233] In one embodiment, a cascaded spinning machine or other spinning machine is arranged to fiberize the melt, and the fibers are entrained in the air as a fiber cloud.

[0234] Many fiber forming devices include a disc or cup that rotates about a substantially vertical axis. Several of these are then routinely arranged in an online configuration in a first direction, as described, for example, in GB-A-926,749, US-A-3,824,086, and WO-A-83 / 03092.

[0235] There is typically an airflow associated with one or each fiberized rotor, in which the fibers are entrained in the air as they leave the rotor surface to form.

[0236] In one embodiment, the aqueous binder composition and / or additives of the present invention are added to the fiber cloud by known means. The amount of binder and / or additives may be the same or different for each spinning machine.

[0237] In one embodiment, the aqueous binder composition and / or additives of the present invention are added to the fiber cloud by known means. The amount of binder and / or additives may be the same or different for each spinning machine.

[0238] As used herein, the term "collection net" is intended to include any mineral fibers that have been collected together on a surface, meaning they are no longer entrained in the air, such as fibrous mineral fibers, granules, clusters, or recycled net waste. A collection net can be a primary net formed by collecting fibers on a conveyor belt and provided as starting material without being cross-laid or otherwise consolidated.

[0239] Alternatively, the collected network may be a secondary network formed by cross-laying or otherwise consolidating the primary network.

[0240] Preferably, the collection net is a primary net.

[0241] Mineral fibre product

[0242] The present invention also relates to mineral fiber products comprising mineral fibers bonded by an adhesive produced by curing an aqueous adhesive composition of the present invention.

[0243] Preferably, the mineral fiber product of the present invention can be obtained by the method according to the present invention.

[0244] The aqueous adhesive compositions and methods have been described above. All indications discussed above regarding the aqueous adhesive compositions and methods, such as mineral fibers, also apply to the mineral fiber products of this invention.

[0245] In a preferred embodiment, the density of the mineral fiber product is 10-1200 kg / m³. 3 Such as 30-800 kg / m 3 Such as 40-600 kg / m 3 Such as 50-250 kg / m 3 Such as 60-200 kg / m 3 Within the range.

[0246] In a preferred embodiment, the mineral fiber product described herein is an insulation product, such as a thermal or sound insulation product, particularly having a strength of 10 to 200 kg / m². 3 The density.

[0247] In an alternative implementation, the mineral fiber product described herein is an exterior wall panel, particularly one with a strength of 1000-1200 kg / m². 3 The density.

[0248] In a preferred embodiment, the loss on ignition (LOI) of the mineral fiber product described herein is in the range of 0.1 to 15.0 wt%, such as 0.3 to 10.0 wt%, such as 0.5 to 8.0 wt%, such as 0.7 to 6.0 wt%.

[0249] Mineral fiber products can be in any conventional form, such as pads or sheets, and can be cut and / or shaped (e.g., into pipe sections) before, during, or after the adhesive has cured.

[0250] As can be seen from the experimental section below (Tables 1-5), when compared with pure PUF adhesive, the cumulative formaldehyde emissions from the cured composite rod (simulated mineral wool product) are greatly reduced by using an aqueous adhesive mixture of PUF adhesive (component (I)) and carbohydrate adhesive (component (II)).

[0251] For composite rods cured at 225°C, the cumulative formaldehyde emission of cured composite rods bonded with the mixed water-based adhesive described herein is equal to or less than 1 μg / g adhesive solids, preferably less than 0.5 μg / g adhesive solids.

[0252] Even low amounts of carbohydrate binder (component (II)) mixed with PUF binder (component (I)) result in a significant reduction in cumulative formaldehyde emissions from composite rods using the curing mixed waterborne binder described herein.

[0253] Those skilled in the art will expect that mineral wool products bonded using a curing mixture of PUF adhesive (component (I)) and carbohydrate adhesive (component (II)) will result in a reduction in formaldehyde emissions from the product according to linear regression, or in other words, a 10% reduction in formaldehyde emissions from cured mineral wool products bonded using the aqueous adhesives described herein, wherein 10% of the PUF adhesive (component (I)) is replaced by 10% of the carbohydrate adhesive (component (II)).

[0254] Surprisingly, however, the actual formaldehyde emission reduction demonstrated by cured composite rods bonded with the inventive water-based adhesive mixture is significantly greater than expected. Therefore, this water-based adhesive mixture system appears to have a synergistic effect on reducing formaldehyde emissions from cured mineral wool products bonded using the inventive water-based adhesive mixture described herein.

[0255] The formaldehyde emissions of cured composite rods bonded with a mixture of PUF adhesive (component (I)) and carbohydrate adhesive (component (II)) were comparable (on the same order of magnitude) to those of formaldehyde-free composite rods made with a commercial adhesive (C2).

[0256] This indicates that even when the inventive mixed waterborne PUF adhesive (component (I)) described herein is applied to mineral wool products with carbohydrate adhesive (component (II)), mineral wool products bonded with the cured inventive adhesive can be obtained, which have formaldehyde emission values ​​that meet the standard (ISO 16000) for formaldehyde-free mineral wool products.

[0257] Applications

[0258] The present invention also relates to the use of aqueous adhesive compositions in the production of mineral fiber products.

[0259] The present invention also relates to the use of aqueous adhesive compositions for reducing formaldehyde and / or ammonia and / or phenol emissions during the production of mineral fiber products.

[0260] Preferably, this use is carried out in the method described above.

[0261] The present invention also relates to the use of water-based adhesive compositions for reducing formaldehyde emissions from cured mineral fiber products.

[0262] Preferably, this use is carried out in the method described above.

[0263] The present invention also relates to a method for reducing formaldehyde and / or ammonia and / or phenol emissions during the application of a phenol-urea-formaldehyde adhesive (PUF adhesive) to mineral fibers in a spinning chamber, the method comprising the following steps:

[0264] - Adding a carbohydrate binder to a PUF binder to obtain an aqueous binder composition, wherein the carbohydrate binder comprises one or more components in the form of carbohydrates (a) and components in the following forms (b):

[0265] (bi) One or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof.

[0266] Component (a) is present in the aqueous adhesive composition in an amount of at least 20% by weight based on the solids content of the adhesive component, and

[0267] - The resulting aqueous adhesive composition is applied to the mineral fibers instead of the PUF adhesive, preferably in the spinning chamber.

[0268] In a preferred embodiment, a method for reducing formaldehyde and / or ammonia and / or phenol emissions during the application of a phenol-urea-formaldehyde adhesive (PUF adhesive) to mineral fibers in a spinning chamber, the method comprising the following steps:

[0269] - Adding a carbohydrate binder to a PUF binder to obtain an aqueous binder composition, wherein the carbohydrate binder comprises one or more components in the form of carbohydrates (a) and components in the following forms (b):

[0270] (bi) one or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof, and

[0271] (bii) One or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof,

[0272] Component (a) is present in the aqueous adhesive composition in an amount of at least 20% by weight based on the solids content of the adhesive component, and

[0273] - The resulting aqueous adhesive composition is applied to the mineral fibers instead of the PUF adhesive, preferably in the spinning chamber.

[0274] The preferred method for reducing formaldehyde and / or ammonia and / or phenol emissions is the method for producing mineral fiber products described herein.

[0275] The above describes the water-based adhesive compositions, methods, and mineral fiber products.

[0276] This invention also relates to a method for reducing formaldehyde emissions from mineral fiber products.

[0277] Specifically, the present invention relates to a method for reducing formaldehyde emissions from mineral fiber products prepared using phenol-urea-formaldehyde adhesive (PUF adhesive), the method comprising the following steps:

[0278] - Add carbohydrate binders to PUF binders to obtain a water-based binder composition.

[0279] The carbohydrate binder comprises one or more carbohydrate components (a) and components in the following forms (b):

[0280] (bi) one or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof, and

[0281] (bii) One or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof,

[0282] Component (a) is present in the aqueous adhesive composition in an amount of at least 20% by weight based on the solids content of the adhesive component.

[0283] - The resulting aqueous binder composition is applied to the mineral fibers, preferably in the spinning chamber, and

[0284] - To cure the water-based adhesive composition.

[0285] The methods and mineral fiber products have been described above.

[0286] Examples

[0287] In the following embodiments, several adhesives were prepared and compared with adhesives according to the prior art.

[0288] Experimental methods and definitions

[0289] General experimental methods

[0290] 75% glucose syrup solution with a DE value of 95 to less than 100 (C Sweet D 02767 (ex Cargill) is supplied by Cargill. 40% Silane (Momentive Silquest) ® VS-142 (hydrolysate of aminoalkylsilane in water) was supplied by Momentive. 28% ammonia solution, 50% hypophosphoric acid solution, and all other components were obtained in high purity from Sigma-Aldrich or TCI. For simplicity, all components whose concentrations are not specified above are assumed to be completely pure and anhydrous.

[0291] Using Mettler Toledo InLab ® Expert Pro-ISM pH electrode and temperature probe from Mettler Toledo SevenCompact TMpH measurement is performed using the S220 pH meter.

[0292] The coarse stone particles (mainly round particles with the same melt composition as asbestos fibers) formed during the cascade spinning process of the asbestos melt in the production of asbestos fibers are obtained from the ROCKWOOL plant in the Netherlands. These coarse stone particles are then processed by ProChem GmbH in Germany to produce clean and sieved stone particles suitable for manufacturing composite rods. In short, the stone particles are heat-treated overnight at 590°C to remove any trace organic matter. After cooling, the stone particles are sieved through 0.50 mm and 0.25 mm sieves. The coarse and fine fractions are discarded, and the remaining stone particles are thoroughly washed several times in deionized water. The sieved and cleaned stone particles are dried and then stored in sealed bags until use. Hereinafter, the obtained stone particles are simply referred to as granules.

[0293] The FUNKTION heat-resistant silicone molds used for manufacturing the rods (each mold has 4×5 slots; top slot dimensions: length = 5.6 cm, width = 2.5 cm; bottom slot dimensions: length = 5.3 cm, width = 2.2 cm; slot height = 1.1 cm) were obtained from F&H of Scandinavia A / S.

[0294] Tested on a Bent Tram SUT 3000 / 520 testing machine (test speed: 10.0 mm / min; fracture level: 50 N; nominal strength: 30 N / mm). 2 Support distance: 40 mm; Maximum deflection: 20 mm; Nominal E modulus: 10000 N / mm 2 Record the three-point bending test on the bar. Place the bar in the machine with the "top surface" (i.e. the surface with dimensions of length = 5.6 cm and width = 2.5 cm) facing upwards.

[0295] Before use, the new foil container used to measure the binder solids content and loss on ignition of the composite rod is heat-treated at 590°C for 15 minutes to remove all organic matter.

[0296] Simulated spinning chamber emissions were generated using an open-type heated tube oven. Emissions from the adhesive sample placed in the tube oven at a given temperature were measured by drawing a constant flow of air through the sample and heated tubes to an MKS2030 FTIR gas analyzer. Spectral data were analyzed using Series 2000 Multigas Analyzer software (version 10.4).

[0297] Samples were analyzed to measure cumulative formaldehyde emissions using an Agilent 1260 HPLC with Infinity mass spectrometer equipped with a Zorbax SB C-18 column (2.1 × 50 mm, 1.8 μm, PN 827700-902) and a Zorbax SB C-18 guard column (4.6 × 5 mm, 1.8 μm, PN 820750-902). Solvent A: H₂O (0.1% formic acid) and solvent B: acetonitrile. Gradient: 65% A (0–1 min), 65% → 20% A (1–9 min), 20% → 65% A (9–11 min). The steel sample holder (accommodating a volume slightly larger than the composite rod) used to suspend the sample above the DNPH solution in a 100 mL blue cap vial was heat-treated at 590 °C for 15 min prior to use to remove all organic matter.

[0298] Binder component solids content - definition

[0299] The weight content of each component in a given adhesive solution prior to curing is based on the anhydrous mass of the component, i.e., excluding solvents, particularly water. The following formula can be used:

[0300]

[0301] If only the solids content of the binder component is calculated, then binder component A will be glucose.

[0302] In calculating the solid content of the binder component in any given binder containing carbohydrates, A could be, for example, glucose and B could be, for example, fructose.

[0303] In the case of PUF adhesives, formaldehyde and ammonia are also considered components of the adhesive. Although these starting materials are volatile, they react at least partially during the preparation of the PUF resin.

[0304] Binder solids - definition and procedure

[0305] The content of the adhesive after curing is called "adhesive solids".

[0306] A disc-shaped asbestos sample (diameter: 5 cm; height: 1 cm) was cut from the asbestos and heat-treated at 590°C for at least 30 minutes to remove all organic matter. The solids content of the adhesive mixture was measured by dispensing a sample (approximately 2 g) of the adhesive mixture onto the heat-treated asbestos disc in a foil container (see mixing examples below). The foil container containing the asbestos disc was weighed immediately before and after the addition of the adhesive mixture. Two such asbestos discs loaded with the adhesive mixture in foil containers were produced and then heated at 200°C for 1 hour (Comparative Adhesive A), at 225°C for 1 hour (Comparative Adhesive A, Comparative Adhesive B, and Comparative Adhesive C), or at 225°C for 2 hours (Comparative Adhesive B and Comparative Adhesive C). After cooling and storing at room temperature for 10 minutes, the sample was weighed and the adhesive solids content was calculated by averaging the two results, and then expressed as a percentage by weight.

[0307] Reaction loss - definition

[0308] Reaction loss is defined as the difference between the solid content of the binder component and the solid content of the binder.

[0309] Manufacture of composite rods (comparative binders A, B and C)

[0310] A 17.5% binder solids solution was obtained as described in the examples below. A sample of the binder solution (70.1 g) was added to the granules (460.0 g) in a mixing bowl at room temperature. The resulting mixture was then mixed using a mixer for approximately 2–5 minutes. The resulting mixture was then filled into 16 slots in a heat-resistant silicone mold used for manufacturing the rods. During the manufacture of each composite rod, the mixture placed in the slots was pressed down as needed and then leveled with a plastic scraper to produce a uniform rod surface. Composite rods made using comparative binder A were cured at 200°C or 225°C for 1 hour, composite rods made using comparative binders B or C were cured at 225°C for 2 hours, and rods made using comparative binder D were cured at 200°C or 225°C for 1 hour. After cooling to room temperature, the composite rods were stored in a climate chamber at 22°C / 50% RH.

[0311] Manufacture of composite rods (comparative binder D)

[0312] A 17.5% binder mixture containing comparative binder A:comparative binder B in a ratio of 75:25, 50:50, or 25:75 was obtained as described in the examples below. A sample (70.1 g) of the binder mixture was added to 460.0 g of granules in a mixing bowl at room temperature. The resulting mixture was then mixed using a mixer for approximately 2–5 minutes. The resulting mixture was then filled into 16 slots in a heat-resistant silicone mold used for manufacturing the rods. During the manufacture of each composite rod, the mixture placed in the slots was pressed down as needed and then leveled with a plastic scraper to produce a uniform rod surface. Rods made using the binder mixture containing comparative binder A:comparative binder B in a ratio of 75:25 were cured at 200°C for 1 hour, and rods made using the binder mixture containing comparative binder A:comparative binder B in a ratio of 50:50 or 25:75 were cured at 225°C for 1 hour. After cooling to room temperature, the composite rods were stored in a climate chamber at 22°C / 50% RH.

[0313] Manufacture of composite rods (binder compositions as described herein)

[0314] A 17.5% binder mixture was obtained as described in the examples below, comprising a ratio of comparative binder A to comparative binder C of 75:25, 50:50, 25:75, or 10:90. A sample (70.1 g) of the binder mixture was added to 460.0 g of granules in a mixing bowl at room temperature. The resulting mixture was then mixed using a mixer for approximately 2–5 minutes. The resulting mixture was then filled into 16 slots in a heat-resistant silicone mold used for manufacturing the rods. During the manufacture of each composite rod, the mixture placed in the slots was pressed down as needed and then leveled with a plastic scraper to produce a uniform rod surface. Rods made using the binder mixture comprising a ratio of comparative binder A to comparative binder C of 75:25 were cured at 200°C or 225°C for 1 hour, and rods made using the binder mixture comprising a ratio of comparative binder A to comparative binder C of 50:50 or 25:75 were cured at 225°C for 1 hour. Rods made using an adhesive mixture containing a 10:90 ratio of comparative adhesive A to comparative adhesive C were cured at 225°C for 2 hours. After cooling to room temperature, the composite rods were stored in a climate chamber at 22°C / 50% RH.

[0315] Aging treatment of composite rods

[0316] The composite rods were aged by subjecting them to either a pressure vessel treatment (15 minutes / 120°C / 1.2 bar) or a water bath treatment (3 hours / 80°C) followed by cooling to room temperature. After initial drying under ambient conditions for one day, the composite rods were stored in a climate chamber at 22°C / 50% RH.

[0317] Measurement of mechanical strength of composite rods

[0318] The maximum load force required to break the composite rod was recorded in a three-point bending test. For each data point, the average value was calculated based on four rods that had undergone the same treatment. The composite rods were stored in a climate chamber at 22°C / 50% RH for at least three days before measuring the maximum load force.

[0319] Measurement of loss on ignition (LOI) of composite rods

[0320] The loss on burn (LOI) of the composite rods was measured by treatment at 590°C in a small foil container. The foil container was weighed, and four rods (typically after failure in a three-point bend test) were placed inside. The assembly was weighed and then heat-treated at 590°C for 30 minutes. After cooling to room temperature, the weight was recorded again, and the LOI was calculated using the following formula:

[0321]

[0322] Water absorption rate measurement

[0323] The water absorption rate of the adhesive is measured as follows: Weigh three rods and immerse them in approximately 250 mL of water in a beaker (565 mL, bottom Ø = 9.5 cm, top Ø = 10.5 cm, height 7.5 cm) for 24 hours. Place the rods side by side on the bottom of the beaker with the "top surface" (i.e., the surface with dimensions of length = 5.6 cm and width = 2.5 cm) facing down. After the specified time, lift each rod one by one and allow it to drip water for one minute. Hold the rod (gently) so that its long side is nearly vertical, allowing water droplets to fall from the corners of the rod. Then weigh the rods and calculate the water absorption rate using the following formula:

[0324]

[0325] Curing properties - DMA (dynamic mechanical analysis) measurements

[0326] A 17.5% binder solids binder solution was obtained as described above. A cut and weighed glass Whatman™ glass microfiber filter (GF / B, 150 mmØ, catalog number 1821 150) (2.5 × 1 cm) was immersed in the 17.5% binder solution for 10 seconds. The resulting binder-soaked filter was then dried in a “sandwich” consisting of: (1) a 0.60 kg 8 × 8 × 1 cm metal plate, (2) four layers of standard filter paper, (3) the binder-soaked glass microfiber filter, (4) four layers of standard filter paper, and (5) the 0.60 kg 8 × 8 × 1 cm metal plate, by applying a weight of 3.21 kg on top of the “sandwich” for approximately 2 × 2 minutes. In a typical experiment, the weight of the cut Whatman™ glass microfiber filter was 0.035 g before the binder was applied and 0.125 g after application and drying.

[0327] DMA measurements were acquired on a Mettler Toledo DMA 1, calibrated at ambient temperature for certified thermometers and certified melting points of indium and tin. The apparatus was operated in single cantilever bending mode; titanium clamps; clamp distance 1.0 cm; temperature band type; temperature range 40–280 °C; heating rate 3 °C / min; displacement 20 μm; frequency 1 Hz; single-frequency oscillation mode. STARe software version 12.00 was used to evaluate the start and end of curing.

[0328] Measurement of simulated spinning room emissions of ammonia and formaldehyde

[0329] A 17.5% binder mixture was obtained in a manner similar to that described in the examples below. Immediately before each emission measurement, approximately 0.70 g of the binder mixture was uniformly distributed onto a binder-free asbestos sample in a small ceramic crucible. Background ammonia and formaldehyde emissions were obtained by initiating emission measurements in an oven heated to 95°C a few minutes before sample insertion. The sample was then loaded into a tubular oven, and a temperature probe was inserted close to the sample to measure the actual temperature. Gas-phase emission IR spectra were then recorded at 95°C for approximately 1 hour at a sampling frequency of 5 seconds. The individual ammonia and formaldehyde concentration time series obtained from the start of the measurement to the disappearance of the water evaporation signal (typically approximately 40 minutes) were integrated to obtain simulated spinning chamber emissions of ammonia, formaldehyde, and phenol. Three measurements were performed for each binder composition, and the emission results were averaged. The results are given as relative emission indices relative to comparative binder A (index 100) in Tables 1-1, 1-2, 1-3, and 1-4.

[0330] Measurement of cumulative formaldehyde emissions from cured binders

[0331] Cumulative formaldehyde emissions from cured composite rods were determined by HPLC-MS of formaldehyde derived from dinitrophenylhydrazine (DNPH). Detection was performed by mass spectrometry. The specific mass of DNPH formaldehyde at 209 m / z was monitored and measured in selected ion monitoring mode.

[0332] After recording the weight of the rod, place the composite rod, i.e., the entire rod, in the support. Then place the sample in a 100 mL blue-capped bottle containing 10 mL of DNPH solution (made from 400 mg of dinitrophenylhydrazine, 50 mg of concentrated sulfuric acid, and acetonitrile to a total volume of 1000 mL). Seal the bottle tightly and seal it with paraffin film.

[0333] Produce enough of these samples to allow for three measurements at 7, 14, and 28 days (thus a total of nine samples for each adhesive). The setup also includes blanks for obtaining background measurements, which are subtracted from the actual sample measurements.

[0334] After the specified time, 1.00 mL of DNPH solution was collected and passed through a 0.22 μ syringe filter. The samples were then analyzed by HPLC (each sample was measured twice), and the amount of formaldehyde captured was determined using a calibration curve obtained from the aldehyde / ketone DNPH stock standard-13 in acetonitrile (Sigma-Aldrich ERA028).

[0335] The data were converted to μg formaldehyde / g binder solids by combining the loss on ignition measurements obtained on unused composite rods with the measured sample weight.

[0336] The measurement results are given in absolute values ​​in Table 1-5.

[0337] Comparative binder compositions from the prior art

[0338] Comparative binder A (phenol-formaldehyde resin modified with urea, PUF-resol)

[0339] Phenol-formaldehyde resin was prepared by reacting 37% formaldehyde solution (606 g) and phenol (189 g) in the presence of 46% potassium hydroxide solution (25.5 g) at a reaction temperature of 84 °C, induced by a heating rate of approximately 1 °C / min. The reaction was continued at 84 °C until the resin achieved an acid resistance of 4 and most of the phenol was converted. Urea (241 g) was then added and the mixture was cooled.

[0340] Acid resistance (AT) indicates the number of times a given volume of adhesive can be diluted with acid without causing the mixture to become cloudy (adhesive precipitation). Sulfuric acid is used to determine the stopping criterion in adhesive production, and an AT of less than 4 indicates the end of the adhesive reaction. To measure AT, a titrant is prepared by diluting 2.5 mL of concentrated sulfuric acid (>99%) with 1 L of deionized water. Then, 5 mL of the adhesive under study is titrated with this titrant at room temperature while keeping the adhesive in motion by hand-shaking; preferably, a magnetic stirrer and magnetic rod are used. Titration continues until a slight turbidity appears in the adhesive, which does not disappear when the adhesive is shaken.

[0341] Acid resistance (AT) is calculated by dividing the amount of acid (mL) used for titration by the amount of sample (mL):

[0342] AT = (Titration volume used (mL)) / (Sample volume (mL))

[0343] Using a portion (100.0 g) of the obtained urea-modified phenol-formaldehyde resin, an adhesive was prepared by adding 28% ammonia solution (7.47 g) and ammonium sulfate (1.20 g), followed by water (100.9 g). The adhesive solids content was then measured as described above: 22.0% at 200°C for 1 h (therefore, the reaction loss was 30.2%); and 21.1% at 225°C for 1 h (therefore, the reaction loss was 33.0%). The mixture was then diluted with the desired amount of water and 4% Momentive VS-142 silane (17.5% final adhesive solids solution, 0.2% of the adhesive solids in silane; final pH 9.6).

[0344] Comparative binder B (carbohydrate binder)

[0345] The mixture of 130.0 g of 75% glucose syrup solution in water (133.5 g) was stirred at room temperature until a clear solution (pH 3.9) was obtained. The binder solids were measured as described above: 22.2% at 225°C for 1 hour (therefore, the reaction loss was 40.0%); and 21.2% at 225°C for 2 hours (therefore, the reaction loss was 42.7%). The mixture was then diluted with the required amount of water and 4% Momentive VS-142 silane (17.5% final binder solids solution, 0.2% of the binder solids in silane; final pH 8.5–9.2).

[0346] Comparative binder C (carbohydrate binder), Example CI

[0347] A mixture of 75% glucose syrup (86.6 g), ammonium aminosulfonate (3.25 g), and urea (3.25 g) in water (151.8 g) was stirred at room temperature until a clear solution was obtained. Then, 28% ammonia solution (0.05 g) was added dropwise to pH 7.2. The binder solids were measured as described above: 19.0% at 225°C for 1 hour (therefore, a reaction loss of 34.9%); and 17.8% at 225°C for 2 hours (therefore, a reaction loss of 39.0%). The mixture was then diluted with the desired amount of water and 4% Momentive VS-142 silane (17.5% final binder solids solution, 0.2% of binder solids in silane; final pH 7.0–7.2).

[0348] Comparative binder C (carbohydrate binder), Example C2

[0349] A mixture of 75% glucose syrup (173.2 g), ammonium aminosulfonate (5.20 g), 50% hypophosphoric acid solution (2.60 g), and urea (6.50 g) in water (303.5 g) was stirred at room temperature until a clear solution was obtained. Then, 28% ammonia solution (1.81 g) was added dropwise to pH 7.3. The binder solids were measured as described above: 18.8% at 225°C for 1 hour (therefore, a reaction loss of 35.4%); and 17.9% at 225°C for 2 hours (therefore, a reaction loss of 38.5%). The mixture was then diluted with the desired amount of water and 4% Momentive VS-142 silane (17.5% final binder solids solution, 0.2% of binder solids in silane; final pH 7.2).

[0350] Compare adhesive C, Example C2, which corresponds to the commercial adhesive described in WO2016 / 102444.

[0351] Comparative binder C (carbohydrate binder), Example C3

[0352] A mixture of 75% glucose syrup (86.6 g), ammonium aminosulfonate (1.30 g), 50% hypophosphoric acid solution (2.60 g), and urea (3.25 g) in water (151.8 g) was stirred at room temperature until a clear solution was obtained. Then, 28% ammonia solution (1.90 g) was added dropwise to pH 7.9. The binder solids were measured as described above: 18.6% at 225°C for 1 hour (therefore, a reaction loss of 35.5%); and 18.0% at 225°C for 2 hours (therefore, a reaction loss of 37.6%). The mixture was then diluted with the desired amount of water and 4% Momentive VS-142 silane (17.5% final binder solids solution, 0.2% of binder solids in silane; final pH 7.7–7.9).

[0353] Comparative binder C (carbohydrate binder), Example C4

[0354] A mixture of 75% glucose syrup (86.6 g), 50% hypophosphite solution (3.90 g), and urea (3.25 g) in water (151.8 g) was stirred at room temperature until a clear solution was obtained. Then, 28% ammonia solution (3.07 g) was added dropwise to pH 7.2. The binder solids were measured as described above: 18.3% at 225°C for 1 hour (therefore, a reaction loss of 35.9%); and 17.3% at 225°C for 2 hours (therefore, a reaction loss of 39.4%). The mixture was then diluted with the desired amount of water and 4% Momentive VS-142 silane (17.5% final binder solids solution, 0.2% of binder solids in silane; final pH 6.6–7.2).

[0355] Comparative binder D (binder mixture of comparative binder A: comparative binder B in a ratio of 75:25, 50:50 or 25:75), Examples D1-D3 Binder compositions as described herein

[0356] Add comparative adhesive B (17.5% adhesive solids, measured at 225°C / 1 hour) to comparative adhesive A (17.5% adhesive solids, measured at 225°C / 1 hour) stirred at room temperature. Mix the comparative adhesives on a balance at the desired ratio (A:B 75:25, 50:50, or 25:75) to produce 80 g of final adhesive mixture. After further stirring for 1–2 minutes, use the resulting mixture (pH 9.1–9.4) in subsequent experiments.

[0357] General binder examples (binder mixtures of comparative binder A: comparative binder C in a ratio of 75:25, 50:50, 25:75 or 10:90), Examples 1-7

[0358] Table 1-1 : Binder compositions according to the prior art Table 1-2: Binder compositions according to the prior art using comparative binders A and B

[0359] Add comparative adhesive C (17.5% adhesive solids, measured at 225°C / 1 hour) to comparative adhesive A (17.5% adhesive solids, measured at 225°C / 1 hour) stirred at room temperature. Mix the comparative adhesives on a balance at the desired ratio (A:C 75:25, 50:50, 25:75, or 10:90) to produce 80 g of final adhesive mixture. After further stirring for 1–2 minutes, use the resulting mixture (pH 8.7–9.7) in subsequent experiments.

[0360] The composition of the comparative adhesive and the inventive adhesive, as well as the results obtained through the test procedures, are shown in Tables 1-1 to 1-4 below.

[0361] The cured compositions of the adhesive and the inventive adhesive, and the results obtained by the test procedures, are shown in Tables 1-5 below.

[0362] Table 1-3: Binder mixtures obtained using comparative binders A and C2

[0363]

[0364] [a] The solid component of the adhesive.

[0365] Table 1-4: Binder mixtures obtained using comparative binders A and C

[0366]

[0367]

[0368] [a] The adhesive solids content was measured at 225°C for 1 hour. [b] The solid component of the adhesive.

[0369] Table 1-5: Formaldehyde emissions of cured composite rods obtained using mixtures of comparative binders A and C2

[0370]

[0371]

[0372] [a] The adhesive solids content was measured at 225°C for 1 hour. [b] The solid component of the adhesive.

[0373] Clauses

[0374]

[0375]

[0376] [a] The adhesive solids content was measured at 225°C for 1 hour. [b] The solid component of the adhesive.

[0377] ​

[0378]

[0379] [a] The adhesive solids content was measured at 225°C for 1 hour.

[0380] ​

[0381] Clause 1. An aqueous adhesive composition for mineral fibers, comprising a mixture of the following substances:

[0382] I) Phenol-urea-formaldehyde adhesive (PUF adhesive), and

[0383] II) Carbohydrate binders, comprising:

[0384] Component (a) is in the form of one or more carbohydrates;

[0385] Component (b) is in the following form:

[0386] (bi) one or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof, or

[0387] (bii) one or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof, or

[0388] A mixture of (biii)(bi) and (bii),

[0389] Component (a) is present in an amount of at least 20% by weight based on the solids content of the adhesive component.

[0390] Clause 1a.) Aqueous adhesive compositions for mineral fibers, which are made from a mixture of the following substances:

[0391] I) Phenol-urea-formaldehyde adhesive (PUF adhesive), and

[0392] II) Carbohydrate binders, comprising:

[0393] Component (a) is in the form of one or more carbohydrates;

[0394] Component (b) is in the following form:

[0395] (bii) One or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof,

[0396] Component (a) is present in an amount of at least 20% by weight based on the solids content of the adhesive component.

[0397] Clause 2. The aqueous adhesive composition according to Clause 1 or 1a.) wherein the PUF adhesive and the carbohydrate adhesive are mixed in a certain ratio such that the weight percentage of B, based on the combined weight of A+B, is in the range of 20 to 95% by weight, wherein B is the weight of the adhesive solids of the carbohydrate adhesive and A is the weight of the adhesive solids of the PUF adhesive.

[0398] Clause 3. The aqueous adhesive composition according to Clause 2, wherein the weight percentage of B is in the range of 25 to 90% by weight based on the combined weight of A and B.

[0399] Clause 4. The aqueous adhesive composition according to Clause 2 or 3, wherein, based on the combined weight of A and B, the weight percentage of A is in the range of 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 20 to 40% by weight, or wherein, based on the combined weight of A and B, the weight percentage of B is in the range of 50 to 95% by weight, preferably 55 to 90% by weight, more preferably 60 to 80% by weight.

[0400] Clause 5. The aqueous adhesive composition according to any one of the preceding clauses, wherein the PUF adhesive (component (I)) is a phenol-urea-formaldehyde methylphenol resin adhesive.

[0401] Clause 6. The aqueous adhesive composition according to any one of the preceding clauses, wherein, with respect to the starting materials phenol, formaldehyde and urea used to prepare the PUF adhesive, the molar ratio of phenol to formaldehyde is 1:2.5 to 1:6, preferably 1:3 to 1:5; and / or the amount of urea is 20 to 60% by weight, preferably 30 to 50% by weight, based on the total weight of phenol, formaldehyde and urea.

[0402] Clause 7. The aqueous adhesive composition according to any one of the preceding clauses, wherein the PUF adhesive is modified with or not modified with ammonia, wherein the amount of ammonia is preferably 0 to 6% by weight of the solids of the PUF adhesive component, more preferably 0 to 4% by weight, and even more preferably 0 to 3% by weight.

[0403] Clause 8. The aqueous adhesive composition according to any one of the preceding clauses, wherein the PUF adhesive is modified with ammonia, wherein the amount of ammonia is preferably 0.1 to 6 wt% of the solids of the PUF adhesive component, more preferably 0.5 to 4 wt%, and most preferably 1 to 3 wt%.

[0404] Clause 9. An aqueous adhesive composition according to any one of the preceding clauses, wherein component (a) is one or more carbohydrates having a DE value of 60 to 100, particularly 85 to 100, more particularly 95 to 100.

[0405] Clause 10. An aqueous adhesive composition according to any one of the preceding clauses, wherein component (a) is a glucose syrup having a DE of 60 to 100, particularly 85 to 100, more particularly 95 to 99.

[0406] Clause 11. The aqueous adhesive composition according to any one of the preceding clauses, wherein component (a) is glucose having a DE of 85 to 100.

[0407] Clause 12. An aqueous adhesive composition according to any one of the preceding clauses, wherein component (a) is a hexose, such as fructose, and / or a pentose, such as xylose.

[0408] Clause 13. The aqueous adhesive composition according to any one of the preceding clauses, wherein component (a) is present in an amount of at least 20% to 90% by weight of the solids of the adhesive component, more preferably 40% to 90% by weight of the solids of the adhesive component, and most preferably 60% to 80% by weight of the solids of the adhesive component.

[0409] Clause 14. The aqueous adhesive composition according to any one of the preceding clauses, wherein component (bi) is selected from aminosulfonic acids and any salts thereof, such as ammonium aminosulfonate, calcium aminosulfonate, sodium aminosulfonate, potassium aminosulfonate, magnesium aminosulfonate, cobalt aminosulfonate, nickel aminosulfonate, N-cyclohexylaminosulfonic acid and any salts thereof, such as sodium N-cyclohexylaminosulfonate.

[0410] Clause 15. The aqueous adhesive composition according to any one of the preceding clauses, wherein the component (bii) is selected from hypophosphite and any salt thereof, such as ammonium hypophosphite or sodium hypophosphite.

[0411] Clause 16. The aqueous adhesive composition according to any one of the preceding clauses, wherein the mass ratio of component (bi) to component (bii) is preferably ≥1:1, more preferably 3:1 to 5:1, and most preferably 4:1.

[0412] Clause 17. The aqueous adhesive composition according to any one of the preceding clauses, wherein the proportion of component (b) is in the range of 1 to 15% by weight, particularly 1 to 12% by weight, and more particularly 2 to 10% by weight, based on the solids content of the adhesive components.

[0413] Clause 18. The aqueous adhesive composition according to any one of the preceding clauses, wherein the carbohydrate adhesive (component (II)) further comprises component (c) in the form of ammonia, wherein the amount of ammonia is preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight, based on the solids content of the adhesive component.

[0414] Clause 19. The aqueous adhesive composition according to any one of the preceding clauses, wherein the carbohydrate adhesive (component (II)) further comprises component (d) in the form of urea, wherein the amount of urea is preferably 0.5 to 6% by weight, more preferably 1 to 5% by weight, and even more preferably 2 to 4% by weight, based on the solids content of the adhesive component.

[0415] Clause 20. The aqueous adhesive composition according to any one of the preceding clauses, wherein the adhesive composition further comprises an additive selected from mineral oils, organosilicones and / or silanes.

[0416] Clause 21. A method for producing an adhesive mineral fiber product, comprising the step of contacting the mineral fibers with an aqueous adhesive composition according to any one of claims 1 to 20.

[0417] Clause 22. A method for producing a bonding mineral fiber product according to Clause 21, wherein the method comprises the following steps:

[0418] -The melt used to manufacture raw materials,

[0419] - The melt is fiberized by a fiber forming device to form mineral fibers, wherein the formed mineral fibers are preferably guided into a spinning chamber.

[0420] - Provides mineral fibers in the form of a collection net.

[0421] - An aqueous binder composition is applied to the mineral fibers before, during, or after the collection net is provided to form a mixture of the mineral fibers and the binder composition, wherein the aqueous binder composition is preferably applied by spraying before the collection net is provided, preferably in the spinning chamber.

[0422] - To cure the adhesive composition mixed with mineral fibers.

[0423] Clause 23. A method for producing mineral fiber products according to Clause 21 or Clause 22, wherein curing is carried out at a temperature of 180-360°C, preferably 200-275°C, more preferably 220-250°C.

[0424] Clause 24. A mineral fiber product comprising mineral fibers bonded by an adhesive, said adhesive being produced by curing an aqueous adhesive composition according to any one of Clauses 1 to 20.

[0425] Clause 25. Mineral fiber products that can be obtained by any one of Clauses 21 to 23.

[0426] Clause 26. Use of the aqueous adhesive composition according to any one of Clauses 1 to 20 in the production of mineral fiber products.

[0427] Clause 27. Use of the aqueous adhesive composition according to any one of Clauses 1-20 for reducing formaldehyde and / or ammonia and / or phenol emissions during the production of mineral fiber products.

[0428] Clause 28. A method for reducing formaldehyde emissions and / or ammonia and / or phenol emissions during the application of a phenol-urea-formaldehyde adhesive (PUF adhesive) to mineral fibers in a spinning chamber, said method comprising the steps of:

[0429] - Adding a carbohydrate binder to a PUF binder to obtain an aqueous binder composition, wherein the carbohydrate binder comprises one or more components in the form of carbohydrates (a) and components in the following forms (b):

[0430] (bi) one or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof, or

[0431] (bii) one or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof, or

[0432] A mixture of (biii)(bi) and (bii),

[0433] Component (a) is present in the aqueous adhesive composition in an amount of at least 20% by weight based on the solids content of the adhesive component, and

[0434] - The resulting aqueous binder composition is applied to the mineral fibers instead of the PUF binder, preferably in the spinning chamber.

[0435] The preferred method is the method according to any one of clauses 21-23.

[0436] Clause 29. Use of the aqueous adhesive composition according to any one of Clauses 1-20 for reducing formaldehyde emissions from cured mineral fiber products.

[0437] Clause 30. A method for reducing formaldehyde emissions from mineral fiber products prepared using phenol-urea-formaldehyde adhesive (PUF adhesive), the method comprising the following steps:

[0438] - Add carbohydrate binders to PUF binders to obtain a water-based binder composition.

[0439] The carbohydrate binder comprises one or more carbohydrate components (a) and components in the following forms (b):

[0440] (bi) one or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof, and

[0441] (bii) One or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof,

[0442] Component (a) is present in the aqueous adhesive composition in an amount of at least 20% by weight based on the solids content of the adhesive component.

[0443] - The resulting aqueous binder composition is applied to the mineral fibers, preferably in the spinning chamber, and

[0444] - To cure the water-based adhesive composition.

Claims

1. An aqueous adhesive composition for mineral fibers, comprising a mixture of the following substances: I) Phenol-urea-formaldehyde adhesive (PUF adhesive), and II) Carbohydrate binders, comprising: Component (a) is in the form of one or more carbohydrates; Component (b) is in the following form: (bi) One or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof. Component (a) is present in an amount of at least 20% by weight based on the solids content of the adhesive component.

2. The aqueous adhesive composition according to claim 1, wherein the component (b) of the carbohydrate adhesive further comprises a component (bii), said component (bii) being in the form of one or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof.

3. The aqueous adhesive composition according to claim 1, wherein the PUF adhesive and the carbohydrate adhesive are mixed in a certain ratio such that the weight proportion of B based on the combined weight of A+B is in the range of 20 to 95% by weight, wherein B is the weight of the adhesive solids of the carbohydrate adhesive and A is the weight of the adhesive solids of the PUF adhesive.

4. The aqueous adhesive composition according to claim 2, wherein the weight percentage of B is in the range of 25 to 90% by weight based on the combined weight of A and B.

5. The aqueous adhesive composition according to claim 2 or 3, wherein, based on the combined weight of A and B, the weight percentage of A is in the range of 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 20 to 40% by weight; or wherein, based on the combined weight of A and B, the weight percentage of B is in the range of 50 to 95% by weight, preferably 55 to 90% by weight, more preferably 60 to 80% by weight.

6. The aqueous adhesive composition according to any one of the preceding claims, wherein the molar ratio of phenol to formaldehyde is 1:2.5 to 1:6, preferably 1:3 to 1:5, with respect to the starting materials phenol, formaldehyde and urea used to prepare the PUF adhesive; and / or the amount of urea is 20 to 60% by weight, preferably 30 to 50% by weight, based on the total weight of phenol, formaldehyde and urea.

7. The aqueous adhesive composition according to any one of the preceding claims, wherein the PUF adhesive is modified with ammonia, wherein the amount of ammonia is preferably 0.1 to 6 wt% of the solids of the PUF adhesive component, more preferably 0.5 to 4 wt%, and most preferably 1 to 3 wt%.

8. The aqueous adhesive composition according to any one of the preceding claims, wherein component (a) is one or more carbohydrates having a DE value of 60 to 100, particularly 85 to 100, more particularly 95 to 100.

9. The aqueous adhesive composition according to any one of the preceding claims, wherein the component (a) is a glucose syrup having a DE of 60 to 100, particularly 85 to 100, more particularly 95 to 99.

10. The aqueous adhesive composition according to any one of the preceding claims, wherein the component (a) is glucose having a DE of 85 to 100.

11. The aqueous adhesive composition according to any one of the preceding claims, wherein component (a) is a hexose, such as fructose, and / or a pentose, such as xylose.

12. The aqueous adhesive composition according to any one of the preceding claims, wherein component (a) is present in an amount of at least 20% to 90% by weight of the solids of the adhesive component, more preferably 40% to 90% by weight of the solids of the adhesive component, and most preferably 60% to 80% by weight of the solids of the adhesive component.

13. The aqueous adhesive composition according to any one of the preceding claims, wherein component (bi) is selected from: ammonium aminosulfonate, calcium aminosulfonate, sodium aminosulfonate, potassium aminosulfonate, magnesium aminosulfonate, cobalt aminosulfonate, nickel aminosulfonate, N-cyclohexylsulfamic acid and any salt thereof, such as sodium N-cyclohexylsulfamic acid, or combinations thereof.

14. The aqueous adhesive composition according to any one of the preceding claims, wherein the component (bii) is selected from ammonium hypophosphite or sodium hypophosphite, or a combination thereof.

15. The aqueous adhesive composition according to any one of the preceding claims, wherein, based on the adhesive solids of the carbohydrate adhesive (component II), the component (bi) is in the range of 0.5 to 20% by weight, particularly 1 to 15% by weight, and more particularly 1 to 5% by weight.

16. The aqueous adhesive composition according to any one of the preceding claims, wherein the component (b) is a mixture of (bi) and (bii).

17. The aqueous adhesive composition according to any one of the preceding claims, wherein the mass ratio of component (bi) to component (bii) is preferably ≥1:1, more preferably 3:1 to 5:1, and most preferably 4:

1.

18. The aqueous adhesive composition according to any one of the preceding claims, wherein the proportion of component (b) is in the range of 1 to 15% by weight, particularly 1 to 12% by weight, and more particularly 2 to 10% by weight, based on the solids of the adhesive component of the carbohydrate adhesive (component (II)).

19. The aqueous adhesive composition according to any one of the preceding claims, wherein the carbohydrate adhesive (component (II)) further comprises component (c) in the form of ammonia, wherein the amount of ammonia is preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight, based on the solids content of the adhesive component.

20. The aqueous adhesive composition according to any one of the preceding claims, wherein the carbohydrate adhesive (component (II)) further comprises component (d) in the form of urea, wherein the amount of urea is preferably 0.5 to 6% by weight, more preferably 1 to 5% by weight, and most preferably 2 to 4% by weight based on the solids content of the adhesive component.

21. The aqueous adhesive composition according to any one of the preceding claims, wherein the adhesive composition further comprises an additive selected from mineral oil, organosilicon and / or silane.

22. A method for producing a bonded mineral fiber product, comprising the step of contacting the mineral fibers with an aqueous adhesive composition according to any one of claims 1 to 21.

23. The method for producing a bonding mineral fiber product according to claim 22, wherein the method comprises the following steps: -The melt used to manufacture raw materials, The melt is fiberized using a fiber forming device to form mineral fibers, wherein the formed mineral fibers are preferably guided into a spinning chamber. - Provides mineral fibers in the form of a collection net. - The aqueous binder composition is applied to the mineral fibers before, during, or after the collection net is provided to form a mixture of the mineral fibers and the binder composition, wherein the aqueous binder composition is preferably applied by spraying before the collection net is provided, preferably in the spinning chamber. - To cure the adhesive composition mixed with the mineral fibers.

24. The method for producing mineral fiber products according to claim 21 or 22, wherein the curing is carried out at a temperature of 180-360°C, preferably 200-275°C, more preferably 220-250°C.

25. A mineral fiber product comprising mineral fibers bonded by an adhesive, said adhesive being produced by curing an aqueous adhesive composition according to any one of claims 1 to 21.

26. A mineral fiber product that can be obtained by the method according to any one of claims 22 to 24.

27. Use of the aqueous adhesive composition according to any one of claims 1 to 21 in the production of mineral fiber products.

28. Use of the aqueous adhesive composition according to any one of claims 1 to 21 for reducing formaldehyde and / or ammonia and / or phenol emissions during the production of mineral fiber products.

29. A method for reducing formaldehyde and / or ammonia and / or phenol emissions during the application of a phenol-urea-formaldehyde resin adhesive (PUF adhesive) to mineral fibers in a spinning chamber, the method comprising the steps of: - Add carbohydrate binders to PUF binders to obtain a water-based binder composition. The carbohydrate binder comprises one or more carbohydrate components (a) and components in the following forms (b): (bi) one or more compounds selected from aminosulfonic acids, aminosulfonic acid derivatives, or any salt thereof, and (bii) One or more compounds selected from hypophosphorous acid, hypophosphorous acid derivatives or any salt thereof, Component (a) is present in the aqueous adhesive composition in an amount of at least 20% by weight based on the solids content of the adhesive component, and - The resulting aqueous binder composition is applied to mineral fibers in a spinning chamber.

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