Binder compositions and associated methods

TECHNICAL FIELD [0002] The present disclosure relates to binding compositions for non-woven fibers. In particular, the present disclosure relates to thermosetting polyester binders for non-woven fibers.

BACKGROUND OF THE INVENTION [0003] Fiberglass insulation products generally include mat fiberglass which are held together by a cured polymer thermosetting resol resin. During the manufacture of such products, streams of molten glass are drawn into fibers of varying lengths and then blown into the forming chamber, where they are folded with little order or in different arrangements, as a mat on a movable conveyor. The fibers, while passing through the forming chamber, are still hot after the pulling operation, are sprayed with an aqueous solution of the binder in the form of a resin. The residual heat from the glass fibers and the air flow through the fiber mat during the forming operation will essentially evaporate most of the water from the binder as a resin, leaving the rest of the binder components as a viscous or semi-viscous liquid with a high solids content, forming a "wet coating". A coated fiber mat or wet coating, which is formed in a compressed state under the action of a high speed air stream passing through the mat in the forming chamber, is then discharged from the forming chamber into a transfer zone in which the mat expands in the vertical direction due to the elasticity of the glass fibers. Such vertical expansion may be important in the manufacture of industrially acceptable fiberglass thermal or sound insulation products. The coated mat is then introduced into a curing oven in which heated air is blown through the mat to cure the binding agent and to rigidly bind the glass fibers.

[0004] Phenol-formaldehyde (PF) resins, as well as urea-modified phenol-formaldehyde resins (PFU resins) have been used in conventional methods and the production of binders for glass fiber insulation products has been heavily based on them for the last few years. Although these resins are inexpensive and provide a hardened fiberglass insulation product with desirable physical properties, they can often have a high content of free formaldehyde, and a characteristic or unpleasant odor limiting their use in certain applications. In addition, during the manufacture of fiberglass insulation, there is the potential for formaldehyde emissions and worker exposure. Thus, production equipment that uses PF and PFU resins as the main component of the binder for insulation products often requires the installation of expensive pollution reduction devices to minimize possible worker exposure to formaldehyde emissions and meet certain required Maximum Achieveable Control Technology (MACT) standards . Variants of non-formaldehyde products and methods of making them include: i) adding a formaldehyde scavenger to the binder to reduce or remove free formaldehyde, thereby reducing its subsequent emission and / or smell; ii) allowing longer reaction times for the resin to reduce the free formaldehyde content of the resin product; or iii) use of formaldehyde-free resin compositions.

[0005] However, the use of scavengers can lead to precipitation, due to the lack of solubility of the scavenger itself and / or the scavenger adduct with any remaining formaldehyde, so that additional and often expensive filtration steps are required. In addition, allowing the resin reaction to last for a longer time to obtain target formaldehyde levels results in the resin product having a higher molecular weight at the same time. Such higher molecular weight resins may not have the desired properties for some applications because many of them tend to stick, which causes the binding agent and the glass fiber coated article to stick to the production equipment. Moreover, higher molecular weight PF resins result in a higher "tetradimer" content. Tetradimer is a highly crystalline PF dimer present in phenolic resins produced under alkaline catalysis, which often easily precipitates. Precipitation is even more likely when free formaldehyde in the resin is bound. Precipitation of the tetradimer can lead to clogging of the spray nozzles and formation of sediment in the storage tanks for the resin binder and in the resin itself, which requires its removal.

[0006] For this reason, attention has been paid to non-formaldehyde resin compositions as an alternative to PF and PFU resins, for their use as binders in the production of fiberglass insulation and other products. Suitable binder compositions preferably have physical properties (e.g., viscosity, dilutability and stickiness) and other properties similar to conventional PF and PFU resins, and can be prepared at low cost. For compositions that have a similar cure time and cure temperature profile, while producing a cured glass fiber insulation product with equivalent physical properties, existing production equipment can be used.

SUMMARY OF THE INVENTION [0007] Aqueous binder compositions are described in the claims. In one aspect, the aqueous binder composition is formaldehyde-free. The aqueous binder composition is thermally curable and has an alkaline pH. In one exemplary embodiment, the aqueous binder composition cures to a formaldehyde-free, water-insoluble thermosetting polyester resin. An aqueous binder composition is also described for use in the manufacture of fiber products, including non-woven fiber products, such as fiber products consisting of glass fibers and / or other fibers, including heat resistant fibers and the like. These aqueous binder compositions and related methods of using binder compositions may include one or more of the features or combinations of features described herein. [0008] In one exemplary embodiment, the aqueous binder composition is thermally curable, comprises a polyacid component having acid groups or also derivatives thereof in the form of an anhydride or salt, and a polyhydroxy component having hydroxyl groups, wherein the pH of the binder composition is greater than about 7 , and for example, ranges from about 7 to about 10. In another exemplary embodiment, the composition comprises a polyacid component and a polyhydroxy component, wherein the ratio of the number of molar equivalents of the acid groups or their derivatives in the form of an anhydride or salt present in the polyacid component to the number of molar equivalents of the hydroxyl groups present in the polyhydroxy component is in the range of about 0.6: 1 to about 1.2: 1. In another exemplary embodiment, the composition comprises a polyacid component which is a dicarboxylic acid including, but not limited to, unsaturated aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, unsaturated cyclic dicarboxylic acids, saturated cyclic dicarboxylic acids, and their derivatives similar. In another exemplary embodiment, the composition comprises a polyacid component that is a tricarboxylic acid, including, but not limited to, unsaturated aliphatic tricarboxylic acids, saturated aliphatic tricarboxylic acids, aromatic tricarboxylic acids, unsaturated cyclic tricarboxylic acids, saturated cyclic tricarboxylic acids, and their derivatives the like. In another exemplary embodiment, the composition comprises a polyacid component that is tetracarboxylic, pentacarboxylic and similar polycarboxylic acids, and derivatives thereof in the form of a salt and anhydride, and combinations thereof. It should be noted that any of these polyacids may be optionally substituted with groups such as hydroxyl, halogen, alkoxy and the like. In one exemplary aspect, the composition is a basic composition in which the polyacid component is neutralized by the addition of a base or in which certain salts of the polyacid component are used. In another exemplary embodiment, the composition comprises a polyacid component such as succinic acid, citric acid or fumaric acid and the like that has been neutralized by the addition of a base or is a salt. In another exemplary embodiment, the polyacid component is maleic acid neutralized with, for example, aqueous ammonia. In another exemplary embodiment, the polyacid component is a maleate ammonium salt. In another exemplary embodiment, the polyhydroxy component is partially hydrolyzed poly (vinyl acetate), such as, for example, ELVANOL (available from DuPont Packaging and Industrial Polymers; Wilmington, Delaware; USA) or poly (vinyl alcohol). In another exemplary embodiment, the composition further comprises a catalyst, such as an acid or acid / salt, including inorganic and organic acids and their salts. Examples of organic acids include sulfonic acids and their salts such as para-toluenesulfonic acid, ammonium para-toluenesulfonate, ammonium naphthalenesulfonate and the like. It should be noted that such catalysts may be capable of increasing the rate of ester formation during curing of the binder compositions described herein. In another exemplary embodiment, the composition further comprises a silicon containing compound such as silyl ethers and alkylsilyl ethers. In one aspect, the silicon containing compound is an amino substituted silicon containing compound, including but not limited to gamma-aminopropyltriethoxysilane. It should be noted that the silicon containing compound can serve as a coupling agent when curing the binder compositions described herein.

[0009] In another exemplary embodiment, a method of binding fibers, including non-woven fibers, is described. In an exemplary aspect, the method comprises contacting the fibers with a heat-curable, aqueous binder composition comprising a polyacid component and a polyhydroxy component, as described herein, wherein the pH of the binder composition is higher than 7, or, for example, ranges from about 7 to about 10, and heating the thermally curable aqueous binder composition at an elevated temperature that is sufficient to cure the binder composition to form a polyester. In one aspect, the polyester is substantially insoluble in water. In another aspect, the polyester is thermosetting.

[0010] In another exemplary embodiment, a glass fiber article is described. The glass fiber article contains a composition made by heating a thermosetting aqueous binder composition that has been applied to fibers, such as a non-woven fiber mat. In one aspect, the pH of the binder composition is higher than 7, or, for example, ranges from about 7 to about 10. In one embodiment, the binder composition comprises the polyacid component and polyhydroxy component described herein.

DETAILED DESCRIPTION [0011] In an exemplary embodiment, a formaldehyde-free, thermally curable, alkaline, aqueous binder composition is described. The binder composition comprises a polyacid component having acid groups or their derivatives in the form of an anhydride or salt, and a polyhydroxy component having hydroxyl groups, wherein the pH of the binder composition is higher than 7, or, for example, ranges from about 7 to about

Ten. The composition can be used as a binder for non-woven fibers such as glass fibers in the manufacture of insulation products. In one embodiment, it has been found that when the formaldehyde-free, alkaline, aqueous binder composition comprising a polyacid and polyhydroxy component as described herein is left for several days at room temperature or heated for short periods without the presence of a catalyst capable of accelerating or increasing the reaction rate chemical, water-insoluble thermosetting polyester resin is formed. Thus, it has been found that the polyacid component is capable of reacting with the polyhydroxy component under basic conditions and in the presence of water, without a catalyst, to form a polyester resin.

[0012] In an exemplary embodiment, the formaldehyde-free, thermally curable, alkaline, aqueous binder composition remains substantially unreacted when applied to a substrate, such as a non-woven fiber sample. As a result of heating, the binder is dried and thermal curing is achieved. It is understood that drying and thermal curing may occur in a sequential manner, simultaneously or converging. The term "thermally curable" as used herein is intended to indicate that a structural or morphological change in the aqueous binder occurs when heated, which is sufficient to modify the properties of non-woven fibers to which an effective amount of binder has been applied; such changes include, but are not limited to, covalent reaction of the binder components, increased adhesion of the binder components to the substrate, and hydrogen bonding of the binder components.

[0013] The term "formaldehyde-free" as used herein is intended to mean that the aqueous binder composition is essentially formaldehyde-free and does not release a significant amount of formaldehyde as a result of drying and / or curing; typically, the formaldehyde-free composition contains less than about 1 ppm formaldehyde based on the weight of the composition.

[0014] The term "basic" as used herein is intended to mean a pH of the solution that is higher than about 7, and, for example, ranges from about 7 to about

10.

[0015] The term "aqueous" as used herein includes water and mixtures consisting essentially of water and other water-miscible solvents including, but not limited to, alcohols, ethers, amines, polar aprotic solvents, and the like.

[0016] As used herein, the terms "glass fiber", "non-woven fiber", and "glass fiber" are intended to mean heat resistant fibers suitable for withstanding elevated temperatures, such as mineral fibers, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, some polyester fibers, artificial silk fibers and glass fibers. Such fibers remain essentially unchanged when exposed to temperatures above about 120 ° C.

[0017] In an exemplary embodiment, the formaldehyde-free, thermally curable, basic, aqueous binder composition comprises a polyacid component having acid groups or a derivative thereof in the form of an anhydride or salt. In one aspect, the polyacid component is sufficiently volatile to maximize its ability to remain available for reaction with the polyhydroxy component. The polyacid component may be substituted with other chemical functional groups. It should be noted that other functional groups are selected to minimize their interference with the production or formation of polyester resin. For example, the polyacid component may be a dicarboxylic acid, such as, for example, maleic acid. The inclusion of other suitable polyacid components is contemplated, but not limited to, such as aconitic acid, adipic acid, azelaic acid, butane tetra carboxylic acid dihydride, butane tricarboxylic acid, hexachloroendomethylene tetrahydrophthalic acid, citraconic acid, citric acid, dicyclothinopentadentene-dicyclopentadentene compounds addition of dipentene and maleic acid, endomethylenehexachlorophthalic acid, ethylenediaminetetraacetic acid (EDTA), completely maleinised rosin, maleized tallow fatty acids, fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleized rosin with unsaturated potassium peroxide for alcohol, followed by carboxylic acid, malic acid, bisacid, A or bisphenol F subjected to a Kolbe-Schmidt reaction with carbon dioxide to introduce 3-4 carboxyl groups, oxalic acid, phthalic acid, poly lactic acid, sebacic acid, succinic acid, tartaric acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, trimellitic acid and trimethanesulfonic acid and their anhydrides and salts and their combinations.

[0018] In an exemplary embodiment, the acid groups of the polyacid-formaldehyde-free, thermally curable, alkaline, aqueous binder composition are neutralized with a base, as a result of which they are converted to acid salt groups, prior to their reaction with the hydroxyl groups of the polyhydroxy component, to form a resin polyester. It is understood that complete neutralization, i.e. about 100% on an equivalent basis can eliminate any need for titration or partial neutralization of acid groups in the polyacid component prior to forming the polyester, but it is anticipated that incomplete neutralization would not inhibit the formation of the polyester. As used herein, the term "base" refers to a base that can be substantially volatile or non-volatile under conditions suitable to facilitate the formation of polyester. For example, the base may be a volatile base, such as, for example, aqueous ammonia; alternatively, the base may be a non-volatile base such as, for example, sodium carbonate, other non-volatile bases such as sodium hydroxide, potassium hydroxide and the like are also contemplated. Neutralization can be carried out before or after mixing the polyacid component with the polyhydroxy component.

[0019] In an exemplary embodiment, the formaldehyde-free, thermally curable, basic, aqueous binder composition also includes a polyhydroxy component having hydroxyl groups. In one aspect, the polyhydroxy component is sufficiently volatile to maximize its ability to remain available for reaction with a polyacid component. The polyhydroxy component may be poly (vinyl alcohol), partially hydrolyzed poly (vinyl acetate) or mixtures thereof. For example, when partially hydrolyzed poly (vinyl acetate) functions as a polyhydroxyl component, 87-89% poly (vinyl acetate) hydrolyzed, such as, for example, DuPont ELVANOL 51-05, which has a molecular weight of about 22000-26000, can be used Da and a viscosity of 5.0-6.0 centipoise. Other partially hydrolyzed poly (vinyl acetates) considered useful, but not exclusively, include 87% -89% hydrolysed poly (vinyl acetates) differing from ELVANOL 51-05 in molecular weight and viscosity, such as, for example, DuPont ELVANOL 51-04, ELVANOL 51-08, ELVANOL 50-14, ELVANOL 5222, ELVANOL 50-26 and ELVANOL 50-42; and partially hydrolyzed poly (vinyl acetates) that differ from ELVANOL 51-05 in molecular weight and viscosity and / or degree of hydrolysis, such as, for example, DuPont ELVANOL 51-03 (8689% hydrolysed), ELVANOL 70-14 (hydrolysed in 95.0-97.0%), ELVANOL 70-27 (95.596,5%), ELVANOL 60-30 (90-93% hydrolysed), ELVANOL 70-03 (98.0-98.8% hydrolysed) , ELVANOL 70-04 (98.0-98.8% hydrolysed), ELVANOL 70-06 (98.5-99.2% hydrolysed), ELVANOL 90-50 (99.0-99.8% hydrolysed ) ELVANOL 70-20 (98.5-99.2% hydrolysed), ELVANOL 70-30 (98.5-99.2% hydrolysed), ELVANOL 71-30 (99.0-99.8% hydrolysed) , ELVANOL 70-62 (98.4-99.8% hydrolysed), ELVANOL 70-63 (98.5-99.2 hydrolysed and ELVANOL 70-75 (98.5-99.2% hydrolysed).

[0020] In an exemplary embodiment, the formaldehyde-free, thermally curable, basic, aqueous binder composition may also contain a catalyst capable of increasing the rate of polyester formation during curing of the binder compositions described herein. For example, the catalyst may be an ammonium salt such as, for example, ammonium para-toluene sulfonate or ammonium naphthalene disulfonate. Other catalysts include, but are not limited to, ammonium sulfate, ammonium chloride, sulfuric acid, lactic acid, lead acetate, sodium acetate, calcium acetate, zinc acetate, organotin compounds, titanium esters, antimony trioxide, germanium salts, sodium hypophosphite , sodium phosphite, methanesulfonic acid and para-toluenesulfonic acid and mixtures thereof. Although additional catalysts may be considered, it is understood that the binder compositions described herein do not require or be limited to any particular catalyst composition or amount, and the addition of such compounds is optional.

[0021] In an exemplary embodiment, the formaldehyde-free, thermally curable, alkaline, aqueous binder composition may also contain a silicon-containing coupling agent (e.g., organosilicon oil). Silicon-containing coupling agents are commercially available from Dow-Corning Corporation, Petrarch Systems, and from the General Electric Company. Their formulation and preparation is well known and therefore do not require a detailed description to be provided. For example, the silicon containing coupling agent may be compounds such as silyl ethers and alkylsilyl ethers. In one aspect, the silicon containing compound is an amino-substituted silane, such as, for example, gamma-aminopropyltriethoxysilane (Dow SILQUEST A-1101; Dow Chemical; Midland, Michigan; USA). When silicon-containing coupling agents are used in an exemplary embodiment, they are typically present in the binder composition in an amount in the range of about 0.1 to about 2.0 weight percent on a solids basis of the binder. It is understood that the binder compositions described herein do not require or are limited to any particular silicon-containing compound or amounts thereof, and the addition of such compounds is optional.

[0022] In an exemplary embodiment, the formaldehyde-free, thermally curable, alkaline, aqueous binder composition can be prepared by mixing 10-50 percent by weight of an aqueous solution of a polyacid component, already neutralized or neutralized in the presence of a polyhydroxy component, 10-30 percent by weight of an aqueous solution of the polyhydroxy component, and, if desired, an aqueous catalyst solution capable of increasing the rate of polyester formation during curing, and, if desired, a silicon containing coupling agent. By changing the polyacid component, polyhydroxy component and optional catalyst and silicon-containing coupling agent composition, their initial concentrations and mixing the solution ratio, a wide range of binding solution compositions can be prepared in which the pH of the binding composition is basic, for example in the range of from about 7 to about 10. Thus, by avoiding acidic binder compositions that contribute to corrosion problems in production equipment, the health and compliance benefits provided by the formaldehyde-free composition are achieved. In addition, the basic, formaldehyde-free binder compositions described herein provide the benefits of allowing existing production equipment to be used in a fiberglass plant and eliminating the need to equip such an installation with stainless steel equipment.

[0023] The following examples illustrate the embodiments of the invention in more detail. These examples are provided only for the purpose of illustrating the invention and should not be construed as limiting the invention or creative idea to any particular physical configuration. For example, despite the fact that the ratio of the molar equivalents of the acid groups or their derivatives in the form of an anhydride or salt in the polyacid component to the number of molar equivalents of the hydroxyl groups in the polyhydroxy component ranges from about 0.6: 1 to about 1.2: 1 , it should be understood that in various variations of the embodiments described herein, these ratios may change without affecting the nature of the invention described. EXAMPLE 1 [0024] ELVANOL 51-05 was prepared as a 14.5% solution in water (17.25 g ELVANOL 51-05 per 119 g solution).

EXAMPLE 2 [0025] While stirring, 205 g of water at room temperature was added sequentially

118.5 g of a 14.5% solution of ELVANOL 51-05 (17.2 g) and 76 g of a 30% solution of maleic acid (22.8 g), resulting in approximately 400 g of a clear, colorless solution. To 50 g of ELVANOL 51-05 / maleic acid solution was added 20.3 g of 18% sodium carbonate solution (3.65 g). The resulting mixture was stirred at room temperature to obtain approximately 70.3 g of a turbid solution. This solution had a pH of 8 and consisted of approximately 24.8% ELVANOL 51-05, 32.9% maleic acid and 42.2% sodium carbonate (as a percentage of all dissolved solids) and contained about 12% dissolved substances solids (as a percentage of the total solution weight).

EXAMPLE 3 [0026] To 50 g of an ELVANOL 51-05 / maleic acid solution prepared as described in Example 2, 0.3 g of 18% sodium carbonate solution (0.05 g) was added. The resulting mixture was stirred at room temperature to obtain approximately 50.3 g of solution. This solution consisted of approximately 42.6% ELVANOL 51-05, 56.4% maleic acid and 1.0% sodium carbonate (as a percentage of all dissolved solids) and contained about 10% dissolved solids (as a percentage total weight of the solution).

EXAMPLE 4 [0027] To 50 g of ELVANOL 51-05 / maleic acid solution prepared as described in Example 2, 6 g of a 19% ammonia solution was added. The resulting mixture was stirred at room temperature to obtain approximately 56 g of solution. This solution had a pH of 9.5 and consisted of approximately 43.0% ELVANOL 51-05 and 57.0% maleic acid (as a percentage of total dissolved solids) and contained about 9% dissolved solids (as a percentage of total solution weight).

EXAMPLE 5 [0028] While stirring, 127 g of a 14.5% solution of ELVANOL 51-05 (11.6 g) and 73 g of a solution of 27% ammonium maleate (corresponding to 15.3 g of maleic acid) were successively added to 127 g of water at room temperature. as a solid) and approximately 280 g of a clear, colorless solution was obtained. This solution showed a pH of 7.94 (after 9 days) and consisted of approximately 43% ELVANOL 51-05 and 57% maleic acid (as a percentage of all dissolved solids) and contained about 10% dissolved solids (as a percentage total weight of the solution). After standing for eleven days at room temperature, a hard, insoluble film was observed at the bottom of the reaction flask.

EXAMPLE 6 [0029] To a solution of 50 g ELVANOL 51-05 / ammonium maleate, prepared as described in Example 5, was added 20 g of a 15% solution of ammonium para-toluenesulfonate (3 g). The resulting mixture was stirred for about 5 minutes at room temperature to give approximately 70 g of a clear, colorless solution. This solution had a pH of 8.28 and consisted of approximately 26.5% ELVANOL 51-05, 35.0% maleic acid and 38.5% ammonium para-toluenesulfonate (as a percentage of all dissolved solids) and contained approximately 11% dissolved solids (as a percentage of the total solution weight).

EXAMPLE 7 [0030] To 50 g of the ELVANOL 51-05 / ammonium maleate solution prepared as described in Example 5, 3.3 g of a 15% solution of ammonium para-toluenesulfonate (0.5 g) was added. The resulting mixture was stirred for about 9 minutes at room temperature to give approximately 53.3 g of a clear, colorless solution. This solution had a pH of 8.17 and consisted of approximately 39.1% ELVANOL 51-05, 51.5% maleic acid and 9.4% ammonium para-toluenesulfonate (as a percentage of all dissolved solids) and contained approximately 10% dissolved solids (as a percentage of the total solution weight).

EXAMPLE 8 [0031] While stirring, 148 g of water at room temperature were added sequentially

303 g 14.5% solution of ELVANOL 51-05 (43.9 g), 147 g 27% solution of ammonium maleate (corresponding to 30.9 g maleic acid as a solid), 67 g of a 15% solution of ammonium para-toluenesulphonate (10.0 g) and 2.0 g of SILQUEST A-1101 1 silane to give approximately 667 g of solution. This solution had a pH of 8.61 and consisted of approximately 50.6% ELVANOL 51-05, 35.6% maleic acid, 11.5% ammonium paratoluene sulfonate and 2.3% SILQUEST A-1101 silane (as a percentage of total dissolved solids) and contained about 13% dissolved solids (as a percentage of the total solution weight).

EXAMPLE 9 [0032] While stirring, 162 g of a 14.5% solution of ELVANOL 51-05 (40.0 g), 160 g of a 27% solution of ammonium maleate (corresponding to 33.6 g of maleic acid) were successively added to 162 g of water at room temperature. as a solid), 67 g of a 15% solution of ammonium para-toluenesulfonate (10.0 g) and 2.0 g of SILQUEST A-1101 silane to give approximately 667 g of solution. This solution had a pH of 8.60 and consisted of approximately 46.7% ELVANOL 51-05, 39.3% maleic acid, 11.7% ammonium paratoluene sulfonate and 2.3% SILQUEST A-1101 silane (as a percentage of total dissolved solids) and contained about 13% dissolved solids (as a percentage of the total solution weight).

EXAMPLE 10 [0033] While stirring, 54 g of a 14.5% solution of ELVANOL 51-05 (10.4 g), 53 g of a 27% solution of ammonium maleate (corresponding to 11.1 g of maleic acid were added successively to 54 g of water at room temperature as a solid), 20 g of a 15% solution of ammonium para-toluenesulfonate (3 g) and 0.6 g of SILQUEST A-1101 silane to give approximately 200 g of solution. This solution had a pH of 8.58 and consisted of approximately 41.4% ELVANOL 51-05, 44.2% maleic acid, 11.9% ammonium para-toluenesulfonate and 2.4% SILQUEST A-1101 silane (as a percentage of % dissolved solids) and contained about 12% dissolved solids (as a percentage of total solution weight).

EXAMPLE 11 [0034] While stirring, 64 g of a 14.5% solution of ELVANOL 51-05 (9.3 g), 57 g of a 27% solution of ammonium maleate (corresponding to 12.0 g of maleic acid were added successively to 58 g of water at room temperature as a solid), 20 g of a 15% solution of ammonium para-toluenesulfonate (3 g) and 0.6 g of SILQUEST A-1101 silane, to give approximately 200 g of solution. This solution had a pH of 8.59 and consisted of approximately 37.3% ELVANOL 51-05, 48.2% maleic acid, 12.0% ammonium para-toluenesulfonate and 2.4% SILQUEST A-1101 silane (as a percentage of % dissolved solids) and contained about 12% dissolved solids (as a percentage of total solution weight).

EXAMPLE 12 [0035] While stirring, 126 g of a 14.5% solution of ELVANOL 51-05 (11.6 g), 20 g of a 15% solution of ammonium paratoluene sulfonate (3 g), 73 g 27 were added successively to 126 g of water at room temperature. % ammonium maleate solution (corresponding to 15.3 g maleic acid as a solid) and 0.65 g SILQUEST A-1101 silane to give approximately 300 g of a clear, colorless solution. This solution had a pH of 8.15 (after +17 hours) and consisted of approximately 38.0% ELVANOL 5105, 50.1% maleic acid, 9.8% ammonium para-toluenesulfonate and 2.1% SILQUEST A-1101 silane (as a percentage of total dissolved solids) and contained about 10% dissolved solids (as a percentage of total solution weight).

EXAMPLE 13 [0036] While stirring, 126 g of a 14.5% solution of ELVANOL 51-05 (11.6 g), 73 g of a 27% solution of ammonium maleate (corresponding to 15.3 g of maleic acid) were successively added to 126 g of water at room temperature. as a solid), 120 g of a 15% solution of ammonium para-toluenesulfonate (18 g) and 0.63 g of SILQUEST A-1101 silane to give approximately 400 g of a clear, colorless solution. This solution had a pH of 7.91 (after +17 hours) and consisted of approximately 25.5% ELVANOL 51-05, 33.6% maleic acid, 39.5% ammonium para-toluenesulfonate and 1.4% SILQUEST A silane -1101 (as a percentage of total dissolved solids) and contained about 11% dissolved solids (as a percentage of total solution weight).

EXAMPLE 14 [0037] While stirring, 126 g of a 14.5% solution of ELVANOL 51-05 (11.6 g), 73 g of a 27% solution of ammonium maleate (corresponding to 15.3 g of maleic acid) were successively added to 126 g of water at room temperature. as a solid), 10 g of a 30% solution of ammonium naphthalene disulfonate (3 g) and 0.6 g of SILQUEST A-1101 silane to give approximately 290 g of a clear, colorless solution. This solution had a pH of 7.89 (after +17 hours) and consisted of approximately 38.0% ELVANOL 51-05, 50.2% maleic acid, 9.8% ammonium naphthalene disulfonate and 2.0% SILQUEST A1101 silane (as % on total dissolved solids) and contained about 10% dissolved solids (as a percentage of total solution weight).

EXAMPLE 15 [0038] To 81 g of a 51% solution of phenolic formaldehyde T 2894 (41.3 g) was added 35 g of a 40% urea solution (14 g). The resulting solution was mixed at room temperature, followed by the addition of 251 g water, 7.9 g 19% ammonia solution, 23.3 g 15% ammonium para-toluenesulfonate solution (3.5 g), and 1.05 g SILQUEST A silane -1101 and approximately 400 g of a clear, colorless solution was obtained. This solution had a pH of 8.14 and consisted of approximately 69.0% T 2894 phenol formaldehyde resin, 23.4% urea, 5.8% ammonium para-toluenesulfonate and 1.8% SILQUEST A-1101 silane (as a percentage of to all dissolved solids) and contained about 15% dissolved solids (as a percentage of total solution weight).

EXAMPLE 16 [0039] To 112.98 g of a 25.3% solution of Rohm-Haas T SET # 1 (28.6 g) was added 77.58 g of water, resulting in approximately 190.56 g of a clear, colorless solution. This solution, consisting of 100% T SET # 1 (as a percentage of all dissolved solids) had a pH of 4.08 and contained about 15% dissolved solids (as a percentage of total solution weight).

EXAMPLE 17 [0040] To 99.75 g of Rohm-Haas T SET # 1 solution prepared as described in Example 16, 0.23 g of SILQUEST A-110 silane was added to give approximately 100 g of a clear, colorless solution. This solution had a pH of 4.06 and consisted of approximately 98.5% T SET # 1 and 1.5% SILQUEST A-1101 silane (as a percentage of total dissolved solids) and contained approximately 15% dissolved solids ( as a percentage of the total solution weight).

EXAMPLE 18 [0041] To evaluate aqueous binder compositions under thermal cure conditions, one or more individual aluminum plates were placed with a 1-g sample of each binder composition. Each binder composition was then placed in one or more of the following firing / curing conditions in preheated ovens to produce a suitable cured binder sample: 0.5 hours at 300 ° F (149 ° C) and 0.5 hours at 350 ° F (177 ° C).

EXAMPLE 19 [0042] For cured binder samples, dry elasticity, dry strength and wet strength were determined, on a scale of 0 corresponding to a lack of 10, corresponding to perfection, as follows: dry elasticity was determined as a degree, in which the binder sample, usually present as a film adhered to the aluminum plate, was resistant to cracking when bending the metal plate. Dry strength was defined as the degree to which the binder sample remained intact and resisted cracking when removed from the preheated oven. Wet strength was defined as the degree to which the binder sample proved to be hardened, as indicated by its tendency to stick to the surface of the aluminum plate as an intact solid mass, and if it did not adhere, it remained intact and resist cracking after adding 10 ml of water and then leaving overnight at room temperature. The complete dissolution of the binder sample in 10 ml of water corresponded to a wet strength value of 0. The appearance of cured binder samples was also determined. The results are shown in Table 1.

Table 1: Test results of cured samples

<td>Example No. (composition as% solid parts)</td><td>Curing Temperature</td><td>Dry elasticity</td><td>Dry strength</td><td>Wet strength</td><td>Ratio COOH / OH</td><td>Look</td>

<td>1 PVA (100%)</td><td>149 ° C</td><td> --</td><td> --</td><td> 0</td><td> --</td><td>Membrane</td>

<td>2 PVA / MA / SC (24.8%: 32.9% : 42.2%)</td><td>149 ° C</td><td> --</td><td> --</td><td> 0</td><td> 1,25</td><td>turbid</td>

<td>3 PVA / MA / SC (42.6%: 56.4% : 1.0%)</td><td>149 ° C</td><td> --</td><td> --</td><td> 5</td><td> 1,25</td><td>Transparent</td>

<td>4 PVA / MA-NH₃(43% : 57%)</td><td>149 ° C</td><td></td><td></td><td> 3</td><td> 1,25</td><td>turbid</td>

<td>5 PVA / AM (43%: 57%)</td><td>149 ° C 177 ° C</td><td> --</td><td> --</td><td> 0 5</td><td> 1,25</td><td>whitish an orange</td>

<td>6 PVA / AM / ATS (26.5%: 35.0% : 38.5%)</td><td>177 ° C</td><td> --</td><td> 10</td><td> 5</td><td> 1,24</td><td>Brudnopomarańczowa</td>

<td>7 PVA / AM / ATS (39.1%: 51.5% : 9.4%)</td><td>177 ° C</td><td> --</td><td> 10</td><td> 5</td><td> 1,24</td><td>śółtopomarańczowa</td>

<td>Example No. (composition as% solid parts)</td><td>Curing Temperature</td><td>Dry elasticity</td><td>Dry strength</td><td>Wet strength</td><td>Ratio COOH / OH</td><td>Look</td>

<td> 8</td><td>149 ° C</td><td> 10</td><td> --</td><td> 0</td><td></td><td>colorless</td>

<td>PVA / AM / ATS / SILQUEST (50.6%: 35.6% : 11.5%: 2.3%)</td><td>177 ° C</td><td> 0</td><td></td><td> 8</td><td> 0,66</td><td>orange-brown</td>

<td> 9</td><td>149 ° C</td><td> 10</td><td> --</td><td> 5</td><td></td><td>colorless</td>

<td>PVA / AM / ATS / SILQUEST (46.7%: 39.3% : 11.7%: 2.3%)</td><td>177 ° C</td><td> 0</td><td></td><td> 8</td><td> 0,79</td><td>bright orange</td>

<td> 10</td><td>149 ° C</td><td> 10</td><td></td><td> 6</td><td></td><td>light brown</td>

<td>PVA / AM / ATS /</td><td>177 ° C</td><td> 10</td><td> --</td><td> 9</td><td> 1,00</td><td> --</td>

<td>SILQUEST (41.4%: 44.2% : 11.9%: 2.4%)</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 11</td><td>149 ° C</td><td>"sticky"</td><td> --</td><td> 1</td><td></td><td>colorless</td>

<td>PVA / AM / ATS / SILQUEST (37.3%: 48.2% : 12.0%: 2.4%)</td><td>177 ° C</td><td></td><td></td><td> 9</td><td> 1,22</td><td>bright orange</td>

<td> 12</td><td>149 ° C</td><td> 10</td><td> 10</td><td> 2</td><td></td><td>whitish</td>

<td>PVA / AM / ATS / SILQUEST (38.0%: 50.1% : 9.8%: 2.1%)</td><td>177 ° C</td><td> 10</td><td> 10</td><td> 8</td><td> 1,24</td><td>orange-brown</td>

<td> 13</td><td>149 ° C</td><td> 10</td><td> 10</td><td> 2</td><td></td><td>whitish</td>

<td>PVA / AM / ATS / SILQUEST (25.5%: 33.6% : 39.5%: 1.4%)</td><td>177 ° C</td><td> 0</td><td> 10</td><td> 5</td><td> 1,24</td><td>brown orange</td>

<td> 14</td><td>149 ° C</td><td> 10</td><td> 10</td><td> 0</td><td></td><td>White</td>

<td>PVA / AM / AND / SILQUEST</td><td>177 ° C</td><td> 10</td><td> 10</td><td> 4</td><td> 1,24</td><td>light brown</td>

<td> (38,0% : 50,2% : 9,8% : 2,0%)</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 15</td><td>149 ° C</td><td> 0</td><td> 10</td><td> 10</td><td></td><td>The yellow</td>

<td>PF / U / ATS / SIL QUEST (69.0%: 23.4%</td><td>177 ° C</td><td> 0</td><td> 10</td><td> 10</td><td></td><td>Matowożółta</td>

<td> : 5,8% : 1,8%)</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Example No. (composition as% solid parts)</td><td>Curing Temperature</td><td>Dry elasticity</td><td>Dry strength</td><td>Wet strength</td><td>Ratio COOH / OH</td><td>Look</td>

<td> 16</td><td>149 ° C</td><td> 10</td><td> 10</td><td> 8</td><td></td><td>colorless</td>

<td>T SET # 1 (100%)</td><td>177 ° C</td><td> 0</td><td> 10</td><td> 8</td><td> --</td><td>colorless</td>

<td> 17</td><td>149 ° C</td><td> 10</td><td> 10</td><td> 8</td><td></td><td>colorless</td>

<td>T SET # 1SILQUEST (98.5%: 1.5%)</td><td>177 ° C</td><td> 0</td><td> 10</td><td> 8</td><td></td><td></td>

PVA = ELVANOL 51-05 (hydrolysed in 87-89% poly (vinyl acetate))

ATS = Ammonium para-toluenesulfonate SC = Sodium carbonate

SILQUEST = Gamma-aminopropyltriethoxysilane (A-1101)

AND = Ammonium naphthalene disulfonate

T-Set # 1 = Formaldehyde-free Rohm-Haas binder

MA = Maleic acid

AS = Ammonium sulfate

NH3 = Aqueous solution of ammonia AM = Ammonium maleate

PF = phenol formaldehyde resin

U = Urea