ES2366648T3 - BINDING COMPOSITIONS AND ASSOCIATED METHODS. - Google Patents

Abstract

A thermally curable aqueous binder composition for fibers, the composition comprising: (a) a polyacid component having acidic groups, or derivatives of anhydride or salt thereof; and (b) a polyhydroxy component having hydroxyl groups; and (c) a silicon-containing compound; wherein the pH of the binder composition is greater than about 7.

Description

Cross reference to related request

This application claims priority under Title 35 of the United States Code, section § 120 (e), to the US patent application. No. 10 / 965,359, filed October 13, 2004, which claims priority under Title 35 of the United States Code, section § 119 (e), to the US provisional patent application. No. 60 / 552,361, filed on March 11, 2004, descriptions of which are incorporated herein by reference in their entirety.

Technical field

The present description relates to binder compositions for nonwoven fibers. In particular, the present description relates to thermally curable polyester binders for nonwoven fibers.

Background of the invention

Fiberglass insulation products generally include mat-shaped glass fibers that are held together by a thermoset and cured polymeric resin. During the production of such products, streams of molten glass are stretched to form fibers of varying lengths and then blown into a formation chamber, where they are deposited with little organization, or in variable patterns, such as a mat on a conveyor belt. The fibers, while in transit in the forming chamber, and while still hot from the stretching operation, are sprayed with an aqueous solution of a resinous binder. The residual heat of the glass fibers and the flow of air through the fibrous mat during the forming operation will generally evaporate most of the water from the resinous binder, thereby leaving the remaining components of the binder on the fibers such as a viscous or semi-viscous liquid of high solids content, thus forming a "wet blanket". The fibrous mat or coated wet blanket, which is formed in a compressed state due to the high velocity of air flow through the mat in the forming chamber, is then transferred out of the formation chamber to a transfer zone where the Mat expands vertically due to the resilience of glass fibers. This vertical expansion may be important in the manufacturing process of commercially acceptable fiberglass thermal or acoustic insulation products. Subsequently, the coated mat is transferred to a curing oven, where heated air is blown through the mat to cure the binder and rigidly adhere the glass fibers to each other.

In conventional procedures, phenol-formaldehyde (PF) resins are used, as well as urea extended phenolformaldehyde resins (PFU resins), and they have been relied on over the past years to prepare binders for insulation products. fiberglass. Although these resins are not expensive and provide the cured fiberglass insulation product with the desired physical properties, they can often have a high content of free formaldehyde, and a distinctive or unpleasant odor that limits their use in certain applications. In addition, during the manufacture of fiberglass insulation, the potential for formaldehyde emissions and worker exposure is present. Therefore, manufacturing facilities that use PF and PFU resins as the main component of the binder for insulation products are often required to install expensive reduction equipment in order to minimize the possible exposure of workers to formaldehyde emissions and meet certain required standards of Maximum Achievable Control Technology (MACT). Options for formaldehyde-free products or procedures include: i) adding a formaldehyde eliminator to the binder to reduce or remove free formaldehyde and thereby limit its subsequent emission and / or odor; ii) allow the resin reaction to proceed for longer periods of time to reduce the free formaldehyde present in the resin product; or iii) use formaldehyde-free resin formulations.

However, the use of eliminators can lead to precipitation, which results from the eliminator itself and / or the adduct between the eliminator and any residual formaldehyde being insoluble, thus requiring additional and often expensive filtration steps. In addition, allowing the resin reaction to proceed for an extended period of time sufficient to provide target levels of formaldehyde results in a resin product having a concomitantly higher molecular weight. Such higher molecular weight resins may lack the desirable properties for some applications, since many tend to be sticky, causing the binder and the binder coated glass fiber product to adhere to the production equipment. In addition, higher molecular weight PF resins tend to have a higher "tetradimer" content. The tetradimer is a highly crystalline PF dimer present in phenolic resins produced under conditions catalyzed with bases, which often precipitates easily. Precipitation is even more likely when free formaldehyde in the resin is removed. Precipitation of the tetradimer may result in the spraying nozzles becoming clogged, and the formation of precipitates in the resin binder storage tanks and in the resin itself, requiring removal.

Therefore, as an alternative to PF and PFU resins, formulations of formaldehyde-free resins have received increasing attention for use as binders in the preparation of fiberglass insulations and other products. Suitable binder formulations advantageously have physical properties (eg, viscosity, dilution and adhesion) and other characteristics similar to conventional PF and PFU resins, and can be prepared at low cost. Formulations that have a curing time and a profile of similar curing temperatures, while providing a cured fiberglass insulation product with equivalent physical properties, may allow the use of existing production equipment.

Compendium of the invention

Aqueous binder compositions are described in the claims. In one aspect, the aqueous binder composition is free of formaldehyde. The aqueous binder composition is thermally curable and has an alkaline pH. In an illustrative embodiment, the aqueous binder composition is cured to a water insoluble thermoset polyester resin free of formaldehyde. An aqueous binder composition for use in the manufacture of fiber products, including nonwoven fiber products such as fiberglass composite fiber products and / or other fibers, including heat resistant fibers and the like, is also described. Aqueous binder compositions and associated methods for using binder compositions may include one or more of the features or combinations of features described herein.

In an illustrative embodiment, the aqueous binder composition is thermally curable, it includes a polyacid component having acid groups, or derivatives of anhydride or salt thereof, and a polyhydroxy component having hydroxyl groups, where the pH of the binder composition is higher that about 7, and is, illustratively, in the range of about 7 to about 10. In another illustrative embodiment, the composition includes a polyacid component and a polyhydroxy component, where the ratio of the number of molar equivalents of acid groups, or derivatives of anhydride or salt thereof, present in the polyacid component, to the number of molar equivalents of hydroxyl groups present in the polyhydroxy component is in the range of about 0.6: 1 to about 1.2: 1. In another illustrative embodiment, the composition includes a polyacid component that is a dicarboxylic acid, which includes, but is not limited to, unsaturated aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, saturated cyclic dicarboxylic acids, saturated cyclic dicarboxylic acids, hydroxyl substituted derivatives thereof, and the like. In another illustrative embodiment, the composition includes a polyacid component that is a tricarboxylic acid, which includes, but is not limited to, unsaturated aliphatic tricarboxylic acids, saturated aliphatic tricarboxylic acids, aromatic tricarboxylic acids, saturated cyclic tricarboxylic acids, cyclic tricarboxylic acids, hydroxyl substituted derivatives thereof, and the like. In another illustrative embodiment, the composition includes a polyacid component which is a tetracarboxylic acid, pentacarboxylic acid and the like polycarboxylic acids, and derivatives of anhydride and salt thereof, and combinations thereof. It is appreciated that any of these polyacids may be optionally substituted, such as with hydroxy, halo, alkyl, alkoxy and the like. In an illustrative aspect, the composition is an alkaline composition, where the polyacid component is neutralized by the addition of a base, or where certain salts of the polyacid component are used. In another illustrative embodiment, the composition includes a polyacid component such as succinic acid, citric acid or fumaric acid and the like, which has been neutralized by the addition of a base, or is a salt. In another illustrative embodiment, the polyacid component is maleic acid neutralized with, for example, aqueous ammonia. In another illustrative embodiment, the polyacid component is the ammonium salt of the maleate. In another illustrative embodiment, the polyhydroxylated component is a partially hydrolyzed polyvinyl acetate, such as, for example, an ELVANOL (available from DuPont Packaging and Industrial Polymers; Wilmington, Delaware; USA), or a poly ( vinyl alcohol). In another illustrative embodiment, the composition further includes a catalyst, such as an acid

or an acid / salt, which includes inorganic and organic acids, and salts thereof. Illustrative organic acids include sulfonic acids and salts thereof, such as para-toluenesulfonic acid, ammonium para-toluenesulfonate, ammonium naphthalenedisulfonate and the like. It is appreciated that such catalysts may be able to increase the rate of ester formation during curing of the binder compositions described herein. In another illustrative embodiment, the composition further includes 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, which includes, but is not limited to, gamma-aminopropyltriethoxysilane. It is appreciated that the silicon-containing compound can serve as a coupling agent during curing of the binder compositions described herein.

In another illustrative embodiment, a method for agglutinating fibers, including nonwoven fibers, is described. In an illustrative aspect, the method includes contacting the fibers with a thermally curable aqueous binder composition, which includes a polyacid component and a polyhydroxy component, such as those described herein, wherein the pH of the binder composition is higher. that 7, or, illustratively, is in the range of about 7 to about 10, and heating the thermally curable aqueous binder composition to an elevated temperature that is sufficient to cure the binder composition to form a polyester. In one aspect, polyester is substantially insoluble in water. In another aspect, polyester is a thermoset polymer.

In another illustrative embodiment, a fiberglass product is described. The fiberglass product includes a composition obtained by heating an aqueous, thermally curable binder composition, which has been applied to fibers, such as a non-woven fiber mat. In one aspect, the pH of the binder composition is greater than 7, or, illustratively, it is in the range of about 7 to about 10. In one embodiment, the binder composition includes a polyacidic component and a polyhydroxylated component as described. In the present memory.

Detailed description of the invention

In an illustrative embodiment, an aqueous, alkaline, thermally curable binder composition free of formaldehyde is described. The binder composition includes a polyacid component having acid groups, or derivatives of anhydride or salt thereof, and a polyhydroxy component having hydroxyl groups, where the pH of the binder composition is greater than 7, or, illustratively, is in the range of about 7 to about 10. The composition can be used as a binder for nonwoven fibers, such as, for example, fiberglass in the manufacture of insulation products. In one embodiment, it has been discovered that when an aqueous, alkaline, formaldehyde-free binder composition, which includes a polyacid component and a polyhydroxy component such as those described herein, is left for several days at room temperature or heated for short periods of time in the absence of a catalyst capable of accelerating or increasing the speed of the chemical reaction, a water insoluble thermoset polyester resin is produced. Therefore, it has been found that a polyacid component is capable of reacting with a polyhydroxy component, under aqueous, alkaline conditions, in the absence of a catalyst, to form a polyester resin.

In an illustrative embodiment, the aqueous, alkaline, thermally curable binder composition, free of formaldehyde, is substantially unreacted when applied to a substrate, such as a sample of nonwoven fibers. With heating, the binder is dried and thermal curing is carried out. It is to be understood that drying and thermal curing can occur sequentially, at one time or concurrently. As used herein, the term "thermally curable" is intended to indicate that a structural change occurs.

or morphological in the aqueous binder with heating, which is sufficient to alter the properties of the nonwoven fibers to which an effective amount of binder has been applied; such changes include, but are not necessarily limited to, covalent reaction of the binder components, improved adhesion of the binder components to the substrate, and hydrogen bonding of the binder components.

The term "formaldehyde free", as used herein, means that the aqueous binder composition is substantially free of formaldehyde, and does not release substantial formaldehyde as a result of drying and / or curing; Typically, less than about 1 ppm of formaldehyde, based on the weight of the composition, is present in a formaldehyde-free composition.

As used herein, the term "alkaline" means a solution pH that is greater than about 7, and is, illustratively, in the range of about 7 to about 10.

As used herein, the term "aqueous" includes water and mixtures composed substantially of water and other solvents miscible with water, which include, but are not limited to, alcohols, ethers, amines, polar aprotic solvents, and the like. .

As used herein, the terms "glass fiber" and "nonwoven fiber" mean heat resistant fibers suitable for resisting high temperatures, such as mineral fibers, aramid fibers, ceramic fibers, metal fibers, fibers. carbon, polyimide fibers, certain polyester fibers, rayon fibers and glass fibers. Such fibers are not substantially affected by exposure to temperatures above about 120 ° C.

In an illustrative embodiment, the aqueous, alkaline, thermally curable, formaldehyde-free binder composition includes a polyacid component having acidic groups, or derivatives of anhydride or salt thereof. In one aspect, the polyacid component is sufficiently nonvolatile 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 is appreciated that the other functional groups are selected to minimize their interference with the preparation or formation of the polyester resin. Illustratively, the polyacid component may be a dicarboxylic acid, such as, for example, maleic acid. Other suitable polyacid components are contemplated, including, but not limited to, aconitic acid, adipic acid, azelaic acid, butanotetracarboxylic acid dihydride, butanotricarboxylic acid, chloréndic acid, citraconic acid, citric acid, dicyclopentadiene maleic acid adducts, acid diethylenetriaminepentaacetic acid, dipentene and maleic acid adducts, endomethylenehexachlorophthalic acid, ethylenediaminetetraacetic acid (EDTA), fully malleted rosin, malleted pine oil fatty acids, fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maned oxide-oxide from potassium to alcohol and then to carboxylic acid, malic acid, mesaconic acid, biphenol A or bisphenol F reacted by the reaction of KOLBE-Schmidt with carbon dioxide to introduce 3-4 carboxyl groups, oxalic acid, phthalic acid, poly ( lactic acid), sebacic acid, succinic acid, á tartaric acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, trimellitic acid, and trimesic acid, and anhydrides and salts thereof, and combinations thereof.

In an illustrative embodiment, the acid groups of the polyacid component of the aqueous, alkaline, thermally curable, formaldehyde-free binder composition are neutralized with a base, and thus converted into acid salt groups, before their reaction with the hydroxyl groups of the polyhydroxylated component to form the polyester resin. It is understood that complete neutralization, that is, approximately 100% calculated on the basis of equivalents, can eliminate any need to titrate or partially neutralize acid groups in the polyacid component before polyester formation, but it is expected that a neutralization less than Complete would not inhibit the formation of polyester. "Base", as used herein, refers to a base that can be substantially volatile or non-volatile under conditions sufficient to promote the formation of polyester. Illustratively, 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, and other non-volatile bases, such as sodium hydroxide, potassium hydroxide and the like are contemplated. The neutralization can be carried out either before or after the polyacid component is mixed with the polyhydroxy component.

In an illustrative embodiment, the aqueous, alkaline, thermally curable, formaldehyde-free binder composition also includes a polyhydroxylated component having hydroxyl groups. In one aspect, the polyhydroxylated component is sufficiently nonvolatile to maximize its ability to remain available for reaction with the polyacid component. The polyhydroxylated component may be a polyvinyl alcohol, a partially hydrolyzed polyvinyl acetate, or mixtures thereof. Illustratively, when a partially hydrolyzed polyvinyl acetate serves as a polyhydroxylated component, a 87-89% hydrolyzed polyvinyl acetate can be used, such as, for example, DuPont ELVANOL 51-05, which has a molecular weight of approximately 22,000-26,000 Da and a viscosity of 5.0-6.0 centipoise. Other partially hydrolyzed polyvinyl acetates contemplated to be useful include, but are not limited to, 87% -89% polyvinyl acetates that differ from ELVANOL 51-05 in molecular weight and viscosity, such as , for example, ELVANOL 51-04, ELVANOL 51-08, ELVANOL 50-14, ELVANOL 52-22, ELVANOL 50-26 and ELVANOL 50-42 from DuPont; and partially hydrolyzed polyvinyl acetates that differ from ELVANOL 51-05 in molecular weight, viscosity and / or degree of hydrolysis, such as, for example, DuPont ELVANOL 51-03 (86-89% hydrolyzed), ELVANOL 70-14 (95.0-97.0% hydrolyzed), ELVANOL 70-27 (95.5-96.5% hydrolyzed), ELVANOL 60-30 (90-93% hydrolyzed), ELVANOL 70-03 (98.0-98.8% hydrolyzed), ELVANOL 70-04 (98.0-98.8% hydrolyzed), ELVANOL 70-06 (98.5-99 hydrolyzed, 2%), ELVANOL 90-50 (hydrolyzed 99.0-99.8%), ELVANOL 70-20 (hydrolyzed 98.5-99.2%), ELVANOL 70-30 (hydrolyzed 98%, 5-99.2%), ELVANOL 71-30 (hydrolyzed 99.0-99.8%), ELVANOL 70-62 (hydrolyzed 98.4-99.8%), ELVANOL 70-63 (hydrolyzed in 98.5-99.2%), and ELVANOL 70-75 (hydrolyzed in 98.5-99.2%).

In an illustrative embodiment, the aqueous, alkaline, thermally curable, formaldehyde-free binder composition may also include a catalyst capable of increasing the rate of polyester formation during curing of the binder compositions described herein. Illustratively, the catalyst may be an ammonium salt, such as, for example, ammonium para-toluenesulfonate or ammonium naphthalenedisulfonate. Other suitable catalysts are contemplated which include, but are not limited to, ammonium sulfate, ammonium chloride, sulfuric acid, lactic acid, lead acetate, sodium acetate, calcium acetate, zinc acetate, organotin compounds, esters of titanium, antimony trioxide, germanium salts, sodium hypophosphite, sodium phosphite, methanesulfonic acid and para-toluenesulfonic acid, and mixtures thereof. Although additional catalysts can be contemplated, it is to be understood that the binder compositions described herein neither require nor are they limited to any particular catalytic composition or amount thereof, and the addition of such compounds is optional.

In an illustrative embodiment, the aqueous, alkaline, thermally curable, formaldehyde-free binder composition may also include a silicon-containing coupling agent (eg, organosilicon oil). Silicon-containing coupling agents have been marketed by the Dow-Corning Corporation, Petrarch Systems, and by the General Electric Company. Its formulation and manufacture are well known, so it is not necessary to provide a detailed description thereof. Illustratively, silicon-containing coupling agents can be compounds such as silyl ethers and alkylsilyl ethers. In one aspect, the silicon-containing coupling agent is an amino substituted silane, such as, for example, gamma-aminopropyltriethoxysilane (SILQUEST A-1101, from Dow; Dow Chemical; Midland, Michigan; USA). When employed in an illustrative embodiment, silicon-containing coupling agents are typically present in the binder composition in an amount within the range of about 0.1 to about 2.0 weight percent based on the solids of the binder. It is to be understood that the binder compositions described herein neither require nor are they limited to any particular silicon-containing compound or amount thereof, and the addition of such compounds is optional.

In an illustrative embodiment, the aqueous, alkaline, thermally curable, formaldehyde-free binder composition can be prepared by mixing a 10-50 weight percent aqueous solution of a polyacid component, already neutralized or neutralized in the presence of the polyhydroxylated component, a solution 1030 percent aqueous by weight of a polyhydroxylated component, and, if desired, an aqueous solution of a catalyst capable of increasing the rate of polyester formation during curing, and also, if desired, a coupling agent containing silicon. By varying the polyacid component, the polyhydroxy component and the optional catalyst and silicon-containing coupling compositions, the initial concentrations thereof, and the mixing ratio of the solutions, a wide range of binder compositions in solution can be prepared. , in which the pH of the binder composition is alkaline, and, illustratively, in the range of about 7 to about 10. Therefore, while avoiding acidic binder compositions, which tend to cause corrosion problems in the Manufacturing equipment, health-related and compliance-related benefits provided by a formaldehyde-free composition are maintained. In addition, the alkali-free formaldehyde-free binder compositions described herein provide the advantages of allowing the use of existing manufacturing equipment in fiberglass manufacturing plants and eliminating the need to provide such plants with new steel equipment. stainless.

The following examples illustrate embodiments of the invention in more detail. These examples are provided for illustrative purposes only, and should not be construed as limiting the invention or the inventive concept to any particular physical configuration. For example, although the ratio of the number of molar equivalents of acidic groups, or derivatives of anhydride or salt thereof, in the polyacid component to the number of molar equivalents of hydroxyl groups in the polyhydroxylated component is in the range of about 0.6 : 1 to about 1.2: 1, it is to be understood that, in the variation of the embodiments described herein, these relationships may be altered without affecting the nature of the described invention.

EXAMPLE 1

ELVANOL 51-05 was prepared as a 14.5% solution in water (17.25 g of ELVANOL 51-05 per 119 g of solution).

EXAMPLE 2

To 205 g of water that was stirred at room temperature 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 were successively added (22.8 g) to produce approximately 400 g of a colorless, transparent solution. To 50 g of the ELVANOL 5105 / maleic acid solution was added 20.3 g of an 18% solution of sodium carbonate (3.65 g). The resulting mixture was stirred at room temperature to produce approximately 70.3 g of a cloudy solution. This solution exhibited a pH of 8, and consisted of approximately 24.8% ELVANOL 51-05, 32.9% maleic acid, and 42.2% sodium carbonate (as a relative percentage of total dissolved solids), and contained approximately 12% dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 3

To 50 g of the ELVANOL 51-05 / maleic acid solution, prepared as described in Example 2, 0.3 g of an 18% solution of sodium carbonate (0.05 g) was added. The resulting mixture was stirred at room temperature to produce 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 relative percentage of total dissolved solids), and contained approximately 10% solids dissolved (as a percentage of the total weight of the solution).

EXAMPLE 4

To 50 g of the 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 produce approximately 56 g of solution. This solution exhibited a pH of 9.5, and consisted of approximately 43.0% of ELVANOL 51-05 and 57.0% of maleic acid (as a relative percentage of total dissolved solids), and contained approximately 9% of dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 5

To 127 g of water that was stirred at room temperature was added successively 80 g of a 14.5% solution of ELVANOL 51-05 (11.6 g) and 73 g of a 27% solution of ammonium maleate ( equivalent to 15.3 g of maleic acid solids) to produce approximately 280 g of a colorless, transparent solution. This solution exhibited a pH of 7.94 (after 9 days), and consisted of approximately 43% ELVANOL 51-05 and 57% maleic acid (as a relative percentage of total dissolved solids), and contained approximately 10% of dissolved solids (as a percentage of the 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

To 50 g of the ELVANOL 51-05 / ammonium maleate solution, prepared as described in Example 5, 20 g of a 15% solution of ammonium para-toluenesulfonate (3 g) was added. The resulting mixture was stirred for approximately 5 minutes at room temperature to produce approximately 70 g of a colorless, clear solution. This solution exhibited 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 relative percentage of solids total dissolved), and contained approximately 11% dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 7

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 approximately 9 minutes at room temperature to produce approximately 53.3 g of a colorless, clear solution. This solution exhibited a pH of 8.17, and consisted of approximately 39.1% of ELVANOL 51-05, 51.5% of maleic acid, and 9.4% of ammonium para-toluenesulfonate (as a relative percentage of solids total dissolved), and contained approximately 10% dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 8

To 148 g of water that was stirred at room temperature was added successively 303 g of a 14.5% solution of ELVANOL 51-05 (43.9 g), 147 g of a 27% solution of ammonium maleate ( equivalent to 30.9 g of maleic acid solids), 67 g of a 15% solution of ammonium para-toluenesulfonate (10.0 g), and 2.0 g of SILQUEST A-1101 silane to produce approximately 667 g of dissolution. This solution exhibited a pH of 8.61, and consisted of approximately 50.6% ELVANOL 51-05, 35.6% maleic acid, 11.5% ammonium paratoluenesulfonate, and 2.3% SILQUEST A silane -1101 (as a relative percentage of total dissolved solids), and contained approximately 13% dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 9

To 162 g of water that was stirred at room temperature was added successively 276 g of a 14.5% solution of ELVANOL 51-05 (40.0 g), 160 g of a 27% solution of ammonium maleate ( equivalent to 33.6 g of maleic acid solids), 67 g of a 15% solution of ammonium para-toluenesulfonate (10.0 g), and 2.0 g of SILQUEST A-1101 silane to produce approximately 667 g of dissolution. This solution exhibited a pH of 8.60, and consisted of approximately 46.7% of ELVANOL 51-05, 39.3% of maleic acid, 11.7% of ammonium paratoluenesulfonate, and 2.3% of SILQUEST A silane -1101 (as a relative percentage of total dissolved solids), and contained approximately 13% dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 10

To 54 g of water that was stirred at room temperature was added successively 72 g of a 14.5% solution of ELVANOL 51-05 (10.4 g), 53 g of a 27% solution of ammonium maleate ( equivalent to 11.1 g of maleic acid solids), 20 g of a 15% solution of ammonium para-toluenesulfonate (3 g), and 0.6 g of SILQUEST A-1101 silane to produce approximately 200 g of solution . This solution exhibited 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% silane SILQUEST A-1101 (as a relative percentage of total dissolved solids), and contained approximately 12% of dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 11

To 58 g of water that was stirred at room temperature was added successively 64 g of a 14.5% solution of ELVANOL 51-05 (9.3 g), 57 g of a 27% solution of ammonium maleate ( equivalent to 12.0 g of maleic acid solids), 20 g of a 15% solution of ammonium para-toluenesulfonate (3 g), and 0.6 g of SILQUEST A-1101 silane to produce approximately 200 g of solution . This solution exhibited 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% silane SILQUEST A-1101 (as a relative percentage of total dissolved solids), and contained approximately 12% of dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 12

To 126 g of water that was stirred at room temperature was added successively 80 g of a 14.5% solution of ELVANOL 51-05 (11.6 g), 20 g of a 15% solution of para-toluenesulfonate of ammonium (3 g), 73 g of a 27% solution of ammonium maleate (equivalent to 15.3 g of maleic acid solids), and 0.65 g of SILQUEST A-1101 silane to produce approximately 300 g of a colorless, transparent solution. This solution exhibited a pH of 8.15 (at +17 hours), and consisted of approximately 38.0% ELVANOL 51-05, 50.1% maleic acid, 9.8% ammonium para-toluenesulfonate, and 2.1% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained approximately 10% dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 13

To 126 g of water that was stirred at room temperature was added successively 80 g of a 14.5% solution of ELVANOL 51-05 (11.6 g), 73 g of a 27% solution of ammonium maleate ( equivalent to 15.3 g of maleic acid solids), 120 g of a 15% solution of ammonium para-toluenesulfonate (18 g), and 0.63 g of SILQUEST A-1101 silane to produce approximately 400 g of a colorless, transparent solution. This solution exhibited a pH of 7.91 (at +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-1101 silane (as a relative percentage of total dissolved solids), and contained approximately 11% dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 14

To 126 g of water that was stirred at room temperature was added successively 80 g of a 14.5% solution of ELVANOL 51-05 (11.6 g), 73 g of a 27% solution of ammonium maleate ( equivalent to 15.3 g of maleic acid solids), 10 g of a 30% solution of ammonium naphthalenedisulfonate (3 g), and 0.6 g of SILQUEST A-1101 silane to produce approximately 290 g of a colorless solution , transparent. This solution exhibited a pH of 7.89 (at +17 hours), and consisted of approximately 38.0% ELVANOL 51-05, 50.2% maleic acid, 9.8% ammonium naphthalenedisulfonate, and 2, 0% SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained approximately 10% dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 15

To 81 g of a 51% solution of phenol-formaldehyde resin T-2894 (41.3 g) was added 35 g of a 40% urea solution (14 g). The resulting solution was stirred at room temperature and then 251 g of water, 7.9 g of a 19% solution of ammonia, 23.3 g of a 15% solution of ammonium para-toluenesulfonate (3, 5 g) and 1.05 g of SILQUEST A-1101 silane to produce approximately 400 g of a colorless, transparent solution. This solution exhibited a pH of 8.14, and consisted of approximately 69.0% of phenol-formaldehyde resin T-2894, 23.4% of urea, 5.8% of ammonium para-toluenesulfonate, and 1.8 % SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained approximately 15% dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 16

To 112.98 g of a 25.3% solution of T SET # 1 of Rohm-Haas (28.6 g), 77.58 g of water were added to produce approximately 190.56 g of a colorless solution , transparent. This solution, which consisted of 100% of T SET # 1 (as a relative percentage of total dissolved solids), exhibited a pH of 4.08 and contained approximately 15% of dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 17

To 99.75 g of the Rohm-Haas T SET # 1 solution, prepared as described in Example 16, 0.23 g of SILQUEST A-1101 silane was added to produce approximately 100 g of a colorless solution , transparent. This solution exhibited a pH of 4.06, and consisted of approximately 98.5% of T SET # 1 and 1.5% of SILQUEST A-1101 silane (as a relative percentage of total dissolved solids), and contained approximately 15% of dissolved solids (as a percentage of the total weight of the solution).

EXAMPLE 18

In order to evaluate the aqueous binder compositions under thermal curing conditions, 1 g samples of each binder composition were placed on one or more individual aluminum plates. Each binder composition was then subjected to one or more of the following cooking / curing conditions in preheated stoves to produce the corresponding sample of cured binder: 0.5 hours at 149 ° C (300 ° F) and 0.5 hours at 177 ° C (350 ° F ).

EXAMPLE 19

Dry flexibility, dry strength and wet strength were determined for binder samples cured on a scale ranging from 0, corresponding to none, to 10, corresponding to excellent, as follows: dry flexibility was determined as the degree to which a binder sample, generally present as a film that adheres to the aluminum plate, resists breakage by flexing the metal plate. Dry strength was determined as the degree to which a binder sample remained intact and resisted breakage after removal from a preheated stove. The wet strength was determined as the degree to which a binder sample appeared to have cured, as indicated by its tendency either to adhere to the surface of the aluminum plate as a solid, intact mass, or, if not adherent, to remain intact and resist breakage, after the addition of 10 ml of water and subsequent rest overnight at room temperature. The complete dissolution of a binder sample in 10 ml of water corresponded to a wet strength value of 0. The appearance of the cured binder samples was also determined. The results are presented in Table 1.

Table 1: Test results of cured binder samples

Example No. (composition as% of solids)

Temp cured Dry flexibility Dry strength Wet strength COOH / OH ratio Appearance

1 PVA (100%)

149 ° C - - 0 - Movie

2 PVA / MA / SC (24.8%: 32.9%: 42.2%)

149 ° C - - 0 1.25 Opaque

3 PVA / MA / SC (42.6%: 56.4%: 1.0%)

149 ° C - - 5 1.25 Transparent

4 PVA / MA-NH3 (43%: 47%)

149 ° C  - - 3 1.25 Opaque

5 PVA / AM (43%: 57%)

149ºC 177ºC ---- ---- 0 5 1.25  Whitish orange-yellow

6 PVA / AM / ATS (26.5%: 35.0%: 38.5%)

177 ° C - 10 5 1.24 Dirty orange

7 PVA / AM / ATS (26.5%: 35.0%: 38.5%)

177 ° C - 10 5 1.24 Yellow orange

8 PVA / AM / ATS / SILQUEST (50.6%: 35.6%: 11.5%: 2.3%)

149ºC 177ºC 10 0 ---- 0 8 0.66 Colorless Orange- Brown

9 PVA / AM / ATS / SILQUEST (50.6%: 35.6%: 11.7%: 2.3%)

149ºC 177ºC 10 0 ---- 5 8 0.79 Colorless Light Orange

10 PVA / AM / ATS / SILQUEST (41.4%: 44.2%: 11.9%: 2.4%)

149ºC 177ºC 10 10 ---- 6 9 1.00 Cinnamon clear -

11 PVA / AM / ATS / SILQUEST (37.3%: 48.2%: 12.0%: 2.4%)

149ºC 177ºC "Sticky" - ---- 1 9 1.22 Colorless Light Orange

12 PVA / AM / ATS / SILQUEST (38.0%: 50.1%: 9.8%: 2.1%)

149ºC 177ºC 10 10 10 10 2 8 1.24 Whitish orange-brown

13 PVA / AM / ATS / SILQUEST (25.5%: 33.6%: 39.5%: 1.4%)

149ºC 177ºC 10 0 10 10 2 5 1.24 Off-white brown-orange

14 PVA / AM / AND / SILQUEST (38.0%: 50.2%: 9.8%: 2.0%)

149ºC 177ºC 10 10 10 10 0 4 1.24 White light brown

15 PF / U / ATS / SILQUEST (69.0%: 23.4%: 5.8%: 1.8%)

149ºC 177ºC 0 0 10 10 10 10 - Yellow dark yellow

16 T SET # 1 (100%)

149ºC 177ºC 10 0 10 10 8 8 - Colorless Colorless

17 T SET # 1-SILQUEST (98.5%: 1.5%)

149ºC 177ºC 10 0 10 10 8 8 - Colorless -

PVA = ELVANOL 51-05 (poly (vinyl acetate) partially hydrolyzed at 87-89%) MA = Maleic acid ATS = Ammonium para-toluenesulfonate AS = Ammonium sulfate SC = Sodium carbonate NH3 = Aqueous ammonia SILQUEST = Gamma -aminopropyltriethoxy (A-1101) silane AM = Ammonium maleate AND = Ammonium naphthalenedisulfonate PF = Phenol and formaldehyde resin T-Set # 1 = Rohm-Haas formaldehyde-free binder U = Urea

Claims (32)

1. A thermally curable aqueous binder composition for fibers, the composition comprising:

(to)

a polyacid component having acidic groups, or derivatives of anhydride or salt thereof; Y

(b)

a polyhydroxy component having hydroxyl groups; Y

(C)

a compound containing silicon;

wherein the pH of the binder composition is greater than about 7.

2.

The binder composition of claim 1, wherein the pH of the binder composition is in the range of about 7 to about 10.

3.

The binder composition of claim 1, wherein the ratio of the number of molar equivalents of said acid groups, or derivatives of anhydride or salt thereof, to the number of molar equivalents of said hydroxyl groups is in the range of about 0, 6: 1 to about 1.2: 1.

Four.

The binder composition of claim 1, wherein said fibers are included in a fiberglass insulation product.

5.

The binder composition of claim 1, wherein said fibers comprise glass fibers.

6.

The binder composition of claim 1, wherein said thermally curable aqueous binder composition is thermally curable to a thermosetting polyester resin substantially insoluble in water.

7.

The binder composition of claim 1, wherein said polyacid component is selected from unsaturated aliphatic polycarboxylic acids, saturated aliphatic polycarboxylic acids, aromatic polycarboxylic acids, unsaturated cyclic polycarboxylic acids, saturated cyclic polycarboxylic acids, hydroxy substituted derivatives thereof, and salts and anhydrides thereof, and combinations thereof.

8.

The binder composition of claim 1, further comprising ammonia or a salt thereof.

9.

The binder composition of claim 1, wherein said polyacid component is an ammonium salt of an unsaturated aliphatic polycarboxylic acid.

10.

The binder composition of claim 1, wherein said polyhydroxy component is a polymer polyol.

eleven.

The binder composition of claim 10, wherein said polymer polyol is a polyalkylene polyol or a polyalkenylene polyol.

12.

The binder composition of claim 10, wherein said polymer polyol is selected from partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, and mixtures thereof.

13.

The binder composition of claim 12, wherein said partially hydrolyzed polyvinyl acetate is 87-89% hydrolyzed polyvinyl acetate.

14.

The binder composition of claim 13, wherein the ratio of the number of molar equivalents of said acid groups, or derivatives of anhydride or salt thereof, to the number of molar equivalents of said hydroxyl groups is in the range of about 0, 6: 1 to about 1.2: 1.

fifteen.

The binder composition of claim 1, further comprising a catalyst, said catalyst being capable of increasing the rate of ester formation.

16.

The binder composition of claim 15, wherein said catalyst is a sulfuric acid or a sulfonic acid, or a salt or derivative thereof.

17.

The binder composition of claim 15, wherein said catalyst is selected from ammonium paratoluenesulfonate, ammonium naphthalenedisulfonate, ammonium sulfate, ammonium chloride, sulfuric 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.

18.

The binder composition of claim 1, wherein said silicon-containing compound is an amino-substituted silicon-containing compound.

19.

The binder composition of claim 1, wherein said silicon-containing compound is an ether of

silyl

twenty.

The binder composition of claim 1, wherein said silicon-containing compound is selected from gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and mixtures thereof.

twenty-one.

The thermally curable aqueous fiber binder composition of claim 1; in which,

The polyacid component having acid groups, or derivatives of anhydride or salt thereof, is an ammonium salt of a dicarboxylic acid.

22

The composition of claim 21, wherein the pH of the binder composition is in the range of about 7 to about 10.

2. 3.

The composition of claim 21, wherein the dicarboxylic acid is maleic acid.

24.

The composition of claim 21, wherein the polyhydroxylated component is a partially hydrolyzed polyvinyl acetate.

25.

The composition of claim 24, wherein the partially hydrolyzed polyvinyl acetate is 87-89% hydrolyzed polyvinyl acetate.

26.

The binder composition of claim 21, wherein the ratio of the number of molar equivalents of the carboxylic acid salt groups in the dicarboxylic acid to the number of equivalents of hydroxyl groups in the polyhydroxylated component is in the range of about 0.6: 1 to about 1.2: 1.

27.

A method of agglutinating fibers, comprising:

(to)

contacting said fibers with the thermally curable aqueous binder composition of claim 1; Y

(b)

heating said thermally curable aqueous binder composition to a temperature sufficient to cure the aqueous binder composition.

28.

The method of claim 27, wherein said fibers are nonwoven fibers.

29.

The method of claim 27, wherein said thermally curable aqueous binder composition is thermally curable to a thermoset polyester resin.

30

A fiberglass product comprising a composition prepared by heating fibers comprising glass fibers, coated with a thermally curable aqueous binder composition comprising a polyacidic component having acidic groups, or derivatives of anhydride or salt thereof, a polyhydroxylated component which has hydroxyl groups, and a silicon-containing compound, wherein the pH of the binder composition is greater than about 7.

31.

The fiberglass product of claim 30, wherein the fibers are included in a non-woven fiber mat and the fiberglass product is a fiberglass insulation product.

32

The fiberglass product of claim 30, wherein said thermally curable aqueous binder composition is thermally curable to a thermoset polyester resin.