Curable aqueous composition and use as fiberglass nonwoven binder.
Abstract
THIS INVENTION IS RELATED TO A CURABLE AQUEOUS COMPOSITION WITHOUT FORMALDEHYDE CONTAINING A POLYACIDE, A POLYOL AND OPTIONALLY AN ACCELERATOR CONTAINING PHOSPHORUS. THE COMPOSITION CAN BE USED AS A BINDER OF HEAT-RESISTANT NON-FABRICS SUCH AS NON-FABRIC COMPOSITION OF FIBERGLASS.
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8 claims: 5 independent, 3 dependent
- 1ES 2 109 441 T5 REIVINDICACIONES 1. Una composicioán acuosa curable que incluye (a) un poliaácido polámero que incluye al menos dos grupos de aácido carboxálico, grupos anhádrido o sus sales;(b) un poliol que incluye al menos dos grupos hidroxilo;y (c) un acelerador con contenido en foásforo;en la que la relaciáon del nuámero de equivalentes de dichos grupos de aácido carboxálico, grupos anhádrido o sus sales al nuámero de equivalentes de dichos grupos hidroxilo es de aproximadamente 1/0,01 hasta aproximadamente 1/3, y en la que dichos grupos de aácido carboxálico, grupos anhádrido o sus sales se neutralizan en una medida menor de aproximadamente el 35 % con una base fija.
- 2Una composiciáon acuosa curable seguán la reivindicaciáon 1, en la que dicho poliáacido polámero es un polámero de adiciáon que incluye al menos un monáomero copolimerizado etiláenicamente insaturado con contenido en áacido carboxálico.
- 3Una composiciáon acuosa curable seguán una cualquiera de las reivindicaciones precedentes, en la que dicho poliol es un compuesto con un peso molecular inferior a aproximadamente 1000 con al menos dos grupos hidroxilo.
- 4Una composiciáon acuosa curable seguán una cualquiera de las reivindicaciones precedentes, en la que dicha relaciáon del nuámero de equivalentes de dichos grupos de aácido carboxálico, grupos anhádrido y sus sales al nuámero de equivalentes de dichos grupos hidroxilo es de aproximadamente 1/0,2 hasta aproximadamente 1/1.
- 5Una composicioán acuosa curable seguán una cualquiera de las reivindicaciones precedentes, en la que dicho poliol es una hidroxilamina.
- 6Una composicioán acuosa curable seguán la reivindicaciáon 5, en la que dicha hidroxilamina se selecciona del grupo compuesto por diisopropanolamina, 2-(2-aminoetilamino)etanol, trietanolamina, tris(hidroximetil)-aminometano y dietanolamina.
- 7Una composiciáon acuosa curable seguán una cualquiera de las reivindicaciones 1 a 4, en la que dicho poliol presenta la foármula:(HO-CH(R 3 )CH2)2N-C(O)-(CH2)m-C(O)-N(CH2CH(R 3 )OH)2 en la que R 3 estáa limitado a H en ambos casos o a -CH3 en ambos casos.
- 8Un procedimiento para aglutinar gáenero no tejido resistente al calor o sus fibras resistentes al calor, que incluye:(a) poner en contacto dicho gáenero no tejido o sus fibras con la mencionada composicioán acuosa curable seguán las reivindicaciones 1-8, y (b) calentar dicha composiciáon acuosa curable a una temperatura de aproximadamente 120 ° Chasta aproximadamente 400 ° C. NOTA INFORMATIVA: Conforme a la reserva del art. 167.2 del Convenio de Patentes Europeas (CPE) y a la Disposición Transitoria del RD 2424/1986, de 10 de octubre, relativo a la aplicación del Convenio de Patente Europea, las patentes europeas que designen a España y solicitadas antes del 7-10-1992, no producirán ningún efecto en España en la medida en que confieran proteccián a productos químicos y farmacáuticos como tales. Esta informacioán no prejuzga que la patente estáeonoincluáda en la mencionada reserva.
Independent claims8
357 paragraphs in 34 sections, as filed
IS 2 109 441 T5
DESCRIPTION
Curable aqueous compositions and their use as a binder for fiberglass nonwovens.
The present invention relates to curable aqueous compositions and their use as a binder for glass fiber nonwovens. Specifically, the present invention relates to a formaldehyde-free curable aqueous composition and its use as a binder for heat resistant nonwovens. More specifically, the present invention relates to a composition that contains (a) a polymeric polyacid containing at least two carboxylic acid groups, anhydride groups or their salts; (b) a polyol containing at least two hydroxyl groups; and (c) a phosphorous-containing accelerator, wherein the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups, or their salts to the number of equivalents of said hydroxyl groups is from about 1 / 0.01 to about 1/3, and wherein the carboxyl groups, anhydride groups or their salts are neutralized to a lesser extent than about 35% with a fixed base. The composition can be used as a binder for nonwovens composed of glass fiber or other heat resistant fibers.
Nonwovens are composed of fibers that can be consolidated by purely mechanical means, such as, for example, entanglement caused by needle punching, by an air process and by a wet process; by chemical means, such as, for example, treatment with a polymeric binder; or by a combination of mechanical and chemical means before, during or after the formation of the nonwoven fabric. Some nonwovens are used at temperatures considerably higher than room temperature, such as fiberglass-containing nonwovens that are impregnated with a hot asphalt composition to produce roofing shingles or rolled roofing material. When a nonwoven fabric is contacted with a hot asphalt composition at temperatures of 150-250 ° C, the nonwoven fabric can loosen, shrink, or otherwise distort. Therefore, nonwovens incorporating an aqueous curable composition should basically retain the properties provided by the aqueous curable composition, such as, for example, tensile strength.
Furthermore, the cured composition should not differ fundamentally from essential characteristics of the nonwoven fabric, as would be the case, for example, if the cured composition was too stiff or brittle or became tacky under the processing conditions.
A process to produce a heat resistant nonwoven fabric employing heat resistant fibers and a heat resistant curable aqueous composition that is free of formaldehyde is needed due to existing and proposed legislation aimed at decreasing or eliminating formaldehode.
Document US-A-4 693 847 describes the esterification of a turpentine resin, which is basically a mixture of monocarboxylic acids, with a condensed ring of C20, with a polyol in the presence of a catalytic proportion of an orgaonic acid ester. hypophosphoric, such as 2-ethylhexyl-phosphonic acid.
In US-A-4 658 003 (hydroxy) -phosphinylalkyl (meth) acrylates are described, which can be prepared by the reaction of hypophosphoric acid with a suitable aldehyde or ketone to prepare an α-hydroxyalkyl-phosphorous acid, which It then reacts with acrylic or methacrylic acid to prepare the (meth) acrylates, which can later be homopolymerized or copolymerized.
Document US-A-5 042 986 describes an aqueous treatment solution for cellulosic textiles, the treatment solution containing an aliphatic cyclic hydrocarbon of 4 to 6 carbon atoms with 4 or more carboxyl groups, in which at least two Adjacent carboxyl groups are in a trans configuration to each other. The treatment solution includes a suitable curing agent, which is the alkali metal dihydrogen phosphate or the alkali metal salt of phosphorous, hypophosphorous and polyphosphoric acid. The treatment process is described as advantageous when used with textiles containing 30-100% cellulosic materials.
In US-A-4 820 307; US-A-4 936 865; and US-A-4,975,209 disclose catalysts for the rapid formaldehyde-free esterification and crosslinking of fibrous cellulose in textile form by means of polycarboxylic acids, including saturated, unsaturated, and aromatic acids, as well as alpha-hydroxy acids. The catalysts described are acidic or slightly basic salts selected from the alkali metal dihydrogen phosphates and alkali metal salts of phosphorous, hypophosphorous and polyphosphoric acids.
In US-A-4 795 533 a solid electrolytic membrane containing a mixture is described.
ES 2 109 441 T5 three-component cla prepared by mixing an organic polymer, such as polyvinyl alcohol, an inorganic compound, and a polyorganic acid, such as polyacrylic acid. The inorganic compound is described as selected from a group consisting of phosphaoric acid, sulfuric acid, heteropoly acids, or salts of heteropoly acids. Examples of phosphoaric acids that can be employed include hypophosphoraic acid, metaphosphoaric acid, orthophosphaoric acid, pyrophosphoric acid, and polyphosphatoric acid. In US-A4 076 917 β-hydroxylakylamides and certain polymers thereof are described as curing agents for polymers containing one or more carboxyl or anhydride functions. The β-hydroaxamides are described as effective in solution, aqueous emulsion or powder coat form.
The present invention wants to overcome the problems mentioned above.
According to a first aspect of the present invention, a curable aqueous composition is provided containing (a) a polymeric polyacid containing at least two carboxylic acid groups, anhydride groups or their salts; (b) a polyol containing at least two hydroxyl groups; and (c) a phosphorous-containing accelerator, wherein the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups, or their salts to the number of equivalents of said hydroxyl groups is from about 1 / 0.01 to about 1/3, and wherein said carboxylic acid groups, anhydride groups or their salts are neutralized to a less than about 35% with a fixed base.
Following a second aspect of the present invention, a process is provided for bonding a heat resistant nonwoven fabric or heat resistant fibers thereof that includes: (a) contacting said nonwoven fabric or its fibers with said aqueous composition curable follow the first aspect of the present invention; and (b) heating said curable aqueous composition at a temperature of about 120 ° C to about 400 ° C.
Preferably, said polymeric polyacid is an addition polymer that includes at least one copolymerized, ethylanically unsaturated, carboxylic acid-containing monoomer.
Preferably, said polyol is a compound with a molecular weight of less than about 1000, with at least two hydroxyl groups.
Preferably, said polyol is a hydroxylamine.
Preferably, said hydroxylamine is selected from the group consisting of diisopropanolamine,
2- (2-aminoethylamino) ethanol, triethanolamine, tris (hydroxymethyl) -aminomethane and diethanolamine.
Preferably, the mentioned ratio of the number of equivalents of said carboxylic acid groups, anhydride groups or their salts to the number of equivalents of said hydroxyl group is about 1 / 0.2 to 1/1.
Preferably, said polyol has the formula:
(HO-CH (R<sup>3</sup>) CH2) 2N-C (O) - (CH2) mC (O) -N (CH2CH (R<sup>3</sup>) OH) 2 where R<sup>3</sup> limited to H in both cases or -CH3 in both cases.
None of the references to prior art documents mentioned above discloses a curable aqueous composition without formaldehyde and its use as a binder for heat resistant nonwovens. Furthermore, nowhere is a composition described containing (a) a polymeric polyacid containing at least two carboxylic acid groups, anhydride groups or their salts; (b) a polyol containing at least two hydroxyl groups; and (c) a phosphorous-containing accelerator, wherein the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups, or their salts to the number of equivalents of said hydroxyl groups is from about 1 / 0.01 to about 1/3, and wherein said carboxyl groups, anhydride groups or their salts are neutralized to a lesser than about 35% with a fixed base.
The present invention therefore provides a curable aqueous composition containing (a) a polymeric polyacid containing at least two carboxylic acid groups, anhydride groups or their salts;
(b) a polyol containing at least two hydroxyl groups; and (c) a phosphorous-containing accelerator, wherein the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups, or their salts to the number of equivalents of said hydroxyl groups is from about 1 / 0.01 to about 1/3, and wherein said carboxylic acid groups, anhydride groups or their salts are neutralized to a less than about 35% with a fixed base. Preferably, the polyacid
ES 2 109 441 T5 polymer is an addition polymer containing at least one copolymerized, ethylenically unsaturated, carboxylic acid-containing monomer. Preferably, the polyol is a compound with a molecular weight of less than about 1000 with at least two hydroxyl groups. Preferably the polyol is a hydroxylamine. Preferably, the hydroxylamine is selected from the group consisting of diisopropanolamine, 2- (2-aminoethylamino) ethanol, triethanolamine, tris (hydroxymethyl) -aminomethane and diethanolamine.
Preferably, the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups or their salts to the number of equivalents of said hydroxyl group is about 1 / 0.2 to 1/1.
The present invention further provides a curable aqueous composition that includes (a) a polymeric polyacid containing at least two carboxylic acid groups, anhydride groups or their salts, and (b) a highly reactive polyol containing at least two hydroxyl groups; wherein the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups or their salts to the number of equivalents of said hydroxyl groups is from about 1 / 0.01 to about 1/3, and wherein said groups of Carboxylic acid, anhydride groups or their salts are neutralized to a lesser extent than about 35% with a fixed base. Preferably, the highly reactive polyol has the formula: (HO-CH (R<sup>3</sup>) CH2) 2N-C (O) - (CH2) mC (O) -N (CH2 CH (R<sup>3</sup>) OH) 2 where R<sup>3</sup> limited to H in both cases or -CH3 in both cases.
A formaldehyde-free curable aqueous composition and its use as a binder for heat resistant nonwovens, such as nonwovens composed of glass fiber or other heat resistant fibers is therefore provided by the present invention. A preferred composition of mine contains (a) a polymeric polyacid containing at least two carboxylic acid groups, anhydride groups or their salts; (b) a polyol containing at least two hydroxyl groups; and (c) a phosphorous-containing accelerator.
The invention is therefore based on a curable aqueous composition without formaldehyde and its use as a binder for heat resistant nonwovens. The composition contains (a) a polymeric polyacid containing at least two carboxylic acid groups, anhydride groups or their salts; (b) a polyol containing at least two hydroxyl groups; and (c) a phosphorus-containing accelerator, wherein the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups, or their salts to the number of equivalents of said hydroxyl groups is from about 1 / 0.01 to about 1/3, and wherein said carboxyl groups are neutralized to a less than about 35% with a fixed base. The composition can be used as a binder for heat resistant nonwovens, such as fiberglass composite nonwovens.
The formaldehyde-free curable aqueous composition of this invention is a basic thermoplastic composition, or basic non-cross-linked when applied to a substrate, although deliberate or incidental low levels of cross-linking may occur. By heating the binder, it dries and curing, either consecutively or simultaneously. By curing is meant here a structural or morphological change that is sufficient to modify the properties of a flexible, porous substrate, to which an effective amount of polymeric binder has been applied, such as, for example, covalent chemical reaction, ionic or clustered interaction, better adhesion to the substrate, transformation or inversion of phases, hydrogen bonding and the like.
This invention relates to a curable aqueous composition free of formaldehyde. By "formaldehyde-free composition" it is meant herein that the composition is basically formaldehyde-free, and that it does not release basically formaldehyde as a result of drying and / or curing. To minimize the formaldehyde content of the aqueous-supported composition, it is preferred when preparing a polymer-containing, curable, formaldehyde-free aqueous composition to employ polymerization aids such as initiators, reducing agents, transfer agents. chains, biocides, surfactants and the like, which are themselves free of formaldehyde, They do not generate formaldehyde during the polymerization process and they do not generate or emit formaldehyde during the treatment of heat resistant nonwovens. By "basically formaldehyde-free" is meant herein that when low levels of formaldehyde can be accepted in the aqueous-supported composition, or when there are important reasons for employing aids that generate or emit formaldehyde, basically aqueous-based compositions free of formaldehyde.
The formaldehyde-free curable aqueous composition contains a polymeric polyacid. The polyacid has to be sufficiently non-volatile so that it is basically available for the reaction with the
ES 2 109 441 T5 polyol in the composition during heating and curing operations. The polyacid can be a polyester containing at least two carboxylic acid groups and an addition polymer or oligomer containing at least two functional carboxylic acid copolymerized monomers. The polymeric polyacid is preferably an additive polymer formed of at least one ethylenically unsaturated monoomer. The addition polymer may be in the form of a solution of the addition polymer in an aqueous medium, such as, for example, an alkali-soluble resin that has been solubilized in a base medium; the form of an aqueous dispersion such as, for example, an emulsion polymerized dispersion; or in the form of an aqueous suspension.
"Aqueous" includes here water and mixtures of basically water and water-miscible solvents.
The addition polymer must contain at least two carboxylic acid groups, anhydride groups or their salts. It is possible to use ethyloenically unsaturated carboxylic acids, such as, for example, methacrylic acid, acrylic acid, crotoonic acid, fumaoric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, α, β-methylene glutaric acid, maleic acid, β-methylene glutaric acid. monoalkyl and monoalkyl fumarates; ethyloenically unsaturated anhydrides, such as, for example, maleic anhydride, itacoonic anhydride, acrylic anhydride and methacholic anhydride; and its salts at a level of about 1% to 100% by weight, based on the weight of the addition polymer. The additional ethyloenically unsaturated monomer may include acrylic ester monoomers, including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, butyl methacrylate, isocyl acrylate, hydroxy acrylate. , hydroxyethyl methacrylate and hydroxypropyl methacrylate; acrylamide or substituted acrylamides; styrene or substituted styrenes; butadiene; vinyl acetate or other vinyl osesters; acrylonitrile or methacrylonitrile; and the like.
The addition polymer containing at least two carboxylic acid groups, anhydride groups, or salts thereof may have a molecular weight of from about 300 to about 10,000,000. A molecular weight of from about 1,000 to about 250,000 is preferred. When the additive polymer is an alkali soluble resin with a content of carboxolic acid, anhydride or its salt of from about 5% to about 30% by weight based on the total weight of the additive polymer, a molecular weight of about 10 is preferred. 000 to about 100,000 as higher molecular weight alkali soluble resins produce curable compositions exhibiting excessive viscosity.
When the addition polymer is in the form of an aqueous dispersion or aqueous suspension and low levels of pre-crosslinking or gel content are desired, low levels of multiethyloenic unsaturated monoomers, such as, for example, allyl methacrylate, can be used. Diallyl phthalate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate and the like at a level of about 0.01% to 5% by weight, based on the weight of the emulsion acrylic copolymer.
When the additive polymer is used as an aqueous dispersion, the diameter of the additive polymer particles can range from about 80 nanometers to about 1000 nanometers, measured using a Brookhaven BI-90 Particle Sizer, which employs a dispersion technique of the light. However, polymodal particle size distributions, such as those described in US 4 384 056 and 4 539 361, thus incorporated herein by reference can be employed.
When the addition polymer is presented in the form of an aqueous dispersion, the addition of polymer particles can be composed of two or more copolymers incompatible with each other. These mutually incompatible copolymers may be present in various morphological configurations, such as, for example, core / shell particles, core / shell particles with shell phases that incompletely encapsulate the nucleus, core / shell particles with a multiplicity of nuclei, interpenetrating crosslinked particles and the like.
The addition polymer can be prepared by solution polymerization, emulsion polymerization, or suspension polymerization techniques to polymerize ethyloenically unsaturated monomers that are well known in the art. If desired, emulsion polymerization, anioonic or non-ionic surfactants, or mixtures thereof may be employed. The polymerization can be carried out in various ways, such as, for example, with all of the monomer in the reaction kettle at the beginning of the polymerization reaction, with part of the monomer in the form of an emulsion present in the reaction kettle at the beginning of the reaction. polymerization, and with a small particle emulsion polymer seed present in the reaction kettle at the beginning of the polymerization reaction.
IS 2 109 441 T5
The polymerization reaction to prepare the addition polymer can be initiated by various procedures known to the art, such as, for example, employing the thermal decomposition of an initiator and employing an oxidation-reduction reaction ("redox reaction") to generate radicals. free to carry out polymerization. In another embodiment, the addition polymer can be formed in the presence of phosphorous-containing chain transfer agents, such as, for example, hypophosphorous acid and its salts, as described in US-A-5 077 361 , thus incorporated herein by reference, to incorporate the phosphorous-containing accelerator and the polyacid component in the same molecule.
Chain transfer agents such as mercaptans, polymercaptans, and halogen compounds can be used in the polymerization mixture to moderate the molecular weight of the acrylic emulsion copolymer. Generally, 0% to about 1% by weight, based on the weight of the polymeric binder, of C4-C20 alkyl mercaptan, mercaptopropionic acid or mercaptopropionic acid osters can be employed.
The carboxyl groups of the polyacid component of the formaldehode-free curable aqueous composition are neutralized with fixed base to an extent less than about 35%, calculated on an equivalent basis. The contact of the addition polymer component before, during or after the preparation of the curable aqueous composition, the addition polymer containing two carboxylic acid groups, anhydride groups or their salts, defined here as neutralization, with a fixed base is necessary before treating the nonwoven substrate.
Neutralization of less than about 35% of the carboxylic acid groups is required, calculated on an equivalent basis, with a fixed base. Neutralization of less than about 20% of the carboxylic acid groups, calculated on an equivalent basis, with a fixed base, is preferred. Neutralization of less than about 5% of the carboxylic acid groups, calculated on an equivalent basis, with a fixed base, is most preferred. When dicarboxylic acid semioster or dicarboxylic acid anhydride is used, the acid equivalents are calculated to be equal to those of the corresponding dicarboxylic acid.
"Fixed base" or "permanent base", as used herein, refers to a monovalent base that is essentially non-volatile under treatment conditions, such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, or t-butylammonium hydroxide. The fixed base has to be sufficiently non-volatile so that it remains basically in the composition during the heating and curing operations. Volatile bases, such as, for example, ammonia or volatile lower alkylamines, do not function as the fixed base of this invention, but can be used in addition to the fixed base; they do not contribute to the degree of neutralization required by a fixed base. Polyvalent fixed bases, such as, for example, calcium carbonate, can tend to destabilize an aqueous dispersion, if the addition polymer is used as an aqueous dispersion, but they can be used in small amounts.
The formaldehyde-free curable aqueous composition also contains a polyol containing at least two hydroxyl groups. The polyol has to be sufficiently non-volatile that it remains basically available for reaction with the polyacid in the composition during heating and curing operations. The polyol can be a compound with a molecular weight less than about 1000 with at least two hydroxyl groups, such as, for example, ethylene glycol, glycerol, pentaerythrol, trimethylol propane, sorbitol, sucrose, glucose, resorcinol, catechol, pyrogallol, ureas glycolates, 1,4-cyclohexanediol, diethanolamine, triethanolamine and certain reactive polyols, such as, for example, β-hydroxyalkylamides, such as, for example, bis- [N, N-di (e-hydroxyethyl)] adipamide, as it can be prepared according to the theory of document US-A-4 076 917, or it can be an addition polymer containing at least two hydroxyl groups, such as, for example, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and homopolymers or copolymers hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like.
The ratio of the number of equivalents of carboxyl, anhydride and their salts of the polyacid to the number of equivalents of hydroxyl in the polyol is from about 1 / 0.01 to about 1/3. An excess of equivalents of carboxyl, anhydride and their salts of the polyacid are preferred to the equivalents of hydroxyl in the polyol. The preferable ratio of the number of equivalents of carboxyl, anhydride and their salts of the polyoacid to the number of equivalents of hydroxyl in the polyol is from about 1 / 0.2 to about 1/1. The most preferred ratio of the number of equivalents of carboxyl, anhydride, and their salts of the polyoacid to the number of hydroxyl equivalents in the polyol is from about 1 / 0.2 to about 1 / 0.8.
IS 2 109 441 T5
The formaldehyde-free curable aqueous composition further contains a phosphorous-containing accelerator, which may be a compound with a molecular weight of less than about 1000, such as, for example, a hypophosphate salt of an alkali metal, an alkali metal phosphite, an alkali metal polyphosphate, an alkali metal dihydrogen phosphate, a polyphospharic acid and an alkylphosphanic acid, or it can be an oligoomer or polymer with groups containing phosphorus, such as, for example, polymeric acid additions of acrylic and / or maleic acids formed in the presence of sodium hypophosphite, polymeric additions prepared from ethylenically unsaturated monoamers in the presence of phosphorous chain transfer agents or terminators, and addition polymers containing residues Acid-functional monoamers, such as, for example, copolymerized phospho-ethalic methacrylate and as phosphaonic acid asters, and monomers of copolymerized vinyl sulphoanic acid, and its salts. The phosphorus-containing accelerator can be employed at a level of about 1% to 40% by weight based on the combined weight of the polyacid and polyol. An accelerator level with phosphorus content of approximately
2.5% to about 10% by weight based on the combined weight of the polyacid and the polyol.
The formaldehyde-free curable aqueous composition may further contain conventional treatment components, such as, for example, emulsifiers, pigments, fillers, anti-migration aids, curing agents, coalescers, wetting agents, biocides, plasticizers, organosilanes, agents. anti-foaming, colorants, waxes and antioxidants.
The formaldehyde-free curable aqueous composition can be prepared by mixing the polyacid, polyol, and phosphorous-containing accelerator using conventional mixing techniques. In another embodiment, a carboxy- or anhydride-containing addiction polymer and a polyol may be present in the same addiction polymer, said addiction polymer containing both carboxyl, anhydride, or their hydroxy functional and functional salts. In another embodiment, the salts of the carboxy groups are salts of functional alkanolamines with at least two hydroxyl groups, such as, for example, diethanolamine, triethanolamine, dipropanolamine and di-isopropanolamine. In a further embodiment, the polyol and the phosphorous-containing accelerator can be present in the same addiction polymer, this addiction polymer can be mixed with a polyacid. In yet another embodiment, the carboxy- or anhydride-containing addiction polymer, polyol, and phosphorus-containing accelerator may be present in the same addiction polymer. Other embodiments will be apparent to those skilled in the art. As described hereinbefore, the carboxyl groups of the polyacid can be neutralized to less than about 35% with a fixed base before, during, or after mixing to provide the aqueous composition. The neutralization can be carried out partially during the formation of the polyacid.
In one embodiment of this invention, the curable aqueous formaldehyde-free composition may contain a highly reactive polyol without a phosphorous-containing accelerator. Polyols reactive enough to allow the omission of a phosphorous-containing accelerator can be employed in a composition containing (a) a polymeric polyacid containing at least two carboxylic acid groups, anhydride groups or their salts and (b) a highly reactive polyol containing at least two hydroxyl groups; wherein the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups, or their salts to the number of equivalents of said hydroxyl groups is from about 1 / 0.01 to about 1/3, and wherein the carboxyl groups Anhydride groups or their salts are neutralized to a lesser than about 30% with a fixed base. The composition can be used as a binder for nonwovens composed of glass fiber or other heat resistant fibers and preferably includes a highly reactive polyol, such as, for example, a β-hydroalkylamide with the formula:
[HO (R<sup>3</sup>) 2C (R<sup>2</sup>) 2C-N (R<sup>1</sup>) -C (O) -] nA - [- C (O) -N (R<sup>1</sup>) -C (R<sup>2</sup>) 2C (R<sup>3</sup>) 2OH] n '(I) where A is a bond, hydrogen, or a monovalent or polyvalent organic radical derived from a saturated or unsaturated alkyl radical, wherein the alkyl radical contains 1-60 carbon atoms, such as methyl , ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, eicosyl, triaconthyl, tetraconthyl, pentaconthyl, hexylconthyl, and the like; aryl, for example, mononuclear and dinuclear aryl such as phenyl, naphthyl, and the like; tri-lower alkyleneamine such as trimethyleneamine, triethyleneamine, and the like; or an unsaturated radical containing one or more ethylanic groups [> C = C <] such as ethenyl, 1-methylethenyl, 3-butenyl-1,3-diyl, 2-propenyl-1,2-diyl, lower carboxyalkenyl such as 3-carboxy -2-propenyl and the like, lower alkoxycarbonyl lower alkenyl, such as 3-methoxycarbonyl-2-propenyl and the like; R<sup>1</sup> is hydrogen, lower alkyl of 1-5 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, pentyl and the like, or hydroxy lower alkyl of 1-5 carbon atoms such as hydroxyethyl , 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxy-2-methylpropyl, 5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl and the pentyl isoamers; R<sup>2</sup> yR<sup>3</sup>
ES 2 109 441 T5 are the same or different radicals selected from hydrogen, straight or branched chain lower alkyl of 1-5 carbon atoms or one of the radicals R<sup>2</sup> and one of the radicals R<sup>3</sup> they can join together to form, together with carbon atoms, such as cyclopentenyl, cyclohexyl, and the like; n is an integer with a value of 1 or i 2yn 'is an integer with a value from 0 to 2 or when n' is 0, a polymer or copolymer (that is, n has a value greater than 1, preferably 2 -10) formed from β-hydroxyalkylamide when A is an unsaturated radical.
The preferred reactive polyols are those of Formula (I) above, where R<sup>1</sup> H, lower alkyl, or HO (R<sup>3</sup>) 2C (R<sup>2</sup>) 2C-, n and n 'are each 1, -A- is - (CH2) m is 0-8, preferably 2-8, each is H and the other is H or a C1-C5 alkyl; namely,
HO-CH (R<sup>3</sup>) CH2-N (R<sup>1</sup>) -C (O) - (CH2) mC (O) -N (R<sup>1</sup>) -CH2CH (R<sup>3</sup>) OH (Ia) in which R<sup>1</sup>, R<sup>3</sup> and m have the meanings just indicated.
Examples of the most preferred reactive polyols have the formula:
(HO-CH (R<sup>3</sup>) CH2) 2N-C (O) - (CH2) mC (O) -N (CH2CH (R<sup>3</sup>) OH) 2 (Ib) in which R<sup>3</sup> it is limited to H in both cases or -CH3 in both cases.
Specific examples that match Formula Ib are bis [N, N-di (e-hydroxyethyl)] adipamide, bis [NN-di (e-hydroxypropyl)] azelamide, bis [NN-di (e-hydroxypropyl)] adipamide. , bis [NN-di (e-hydroxypropyl)] glutaramide, bis [NN-di (e-hydroxypropyl)] succinamide and bis [N-methyl-N- (e-hydroxyethyl)] oxamide.
In one embodiment of this invention, the formaldehyde-free curable aqueous composition can be used as a binder for heat resistant nonwovens, such as nonwovens containing heat resistant fibers, such as, for example, non-woven fabrics. made of aramid, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, certain polyether fibers, rayon fibers and glass fibers.
By "heat resistant fibers" it is meant here fibers that are basically unaffected by exposure to temperatures above 125 ° C. Heat resistant nonwovens may also contain fibers that are not themselves heat resistant, such as certain polyether fibers, rayon fibers, nylon fibers, and superabsorbent fibers, as long as they do not materially adversely affect the performance. substrate performance.
The formaldehyde-free curable aqueous composition can be applied to a nonwoven fabric by conventional techniques, such as, for example, air spray or airless spray, impregnation, saturation, roll coating, curtain coating, beater deposition, coagulation or Similar.
The aqueous-supported formaldehyde-free composition, once applied to the nonwoven fabric, is heated to effect drying and curing. The duration and temperature of the heating will affect the drying speed, the workability and the workability and the development of property in the treated substrate. About 120 heat treatment can be done<sup>°</sup>Chasta approximately 400<sup>°</sup>C for a period of time from about 3 seconds to about 15 minutes; treatment is preferred at about 150<sup>°</sup>C up to about 200<sup>°</sup>C. The drying and curing functions can be performed in two or more separate steps, if desired. For example, the composition may first be heated to a temperature and for a time sufficient to dry out the composition but not basically cure the composition, and then heated a second time to a higher temperature and / or for a longer period of time to perform. curing. Such a process, referred to as "step b", can be used to provide binder-treated nonwoven fabric in, for example, roll form, which can be cured at a later stage, without forming or molding or forming or molding into a configuration. special, concomitant to the curing process.
Heat resistant nonwovens can be used in applications such as, for example, insulation rolls or slats, as reinforcing mats for floor or ceiling applications, as wicking, as a microglass-based substrate for printed circuit boards or Pile separators, as a filter, as a tape and as a reinforcing screen in cement and non-cement coatings for masonry.
IS 2 109 441 T5
The present invention will now be described by way of example only.
Example 1
Preparation of the curable aqueous composition. Sample preparation 1
To 178.94 grams of polyacrylic acid (MW = 60,000) were added 11.44 grams of glycerol, 5.62 grams of sodium hypophosphite monohydrate and 4.0 grams of water. The pH of the mixture was 2.1 and the viscosity 208 mNsm.<sup>-2</sup> (centipoise) (measured on a Brookfield LVF viscometer, spindle # 4 at 100rpm). Active ingredients were 30.9% (active ingredients were all components other than water). Sample 1 is a curable aqueous composition according to this invention.
Example 2
Preparation of other curable compositions. Preparation of samples 2-5 and comparison samples AB
Samples 2-5 and comparison samples AB were prepared following sample 1, with the amounts of ingredients indicated in table 2.1.
TABLE 2.1
Preparation of curable aqueous compositions
<td>Show</td><td>Grams of polyacid</td><td>Grams of polyol</td><td>Grams of acceleration.</td><td>H20</td>
<td> 2</td><td>100 polyacrylic acid<sup>1</sup></td><td>40.6 HEA<sup>2</sup></td><td>4.13 SHP<sup>3</sup></td><td> 60,6</td>
<td> 3</td><td>125 polyacrylic acid<sup>4</sup></td><td>15.3 PE<sup>5</sup></td><td>9.8 SHP<sup>3</sup></td><td> 512,3</td>
<td> 4</td><td>140 polyacrylic acid<sup>6</sup></td><td>49.3 HEA<sup>2</sup></td><td>5.5 SHP<sup>3</sup></td><td> 81,7<sup>7</sup></td>
<td> 5</td><td>160 p (AA / MA / SHP)<sup>10</sup></td><td>124.8 HEA<sup>2</sup></td><td>Go away<sup>10</sup></td><td> 266,9</td>
<td>Comp. TO</td><td>92.6 acidic polyacrylic<sup>1</sup></td><td>none</td><td>none</td><td> 43,6</td>
<td>Comp.B</td><td>146.5 acidic polyacrylic<sup>8</sup></td><td>35 HEA<sup>2</sup></td><td>5.4 SHP<sup>3</sup></td><td> 83,2<sup>9</sup></td>
<sup>1</sup> polyacrylic acid of MW = 60,000 with 25% in solids; <sup>2</sup> bis [N, N-di (e-hydroxyethyl) adipamide with 40% solids; <sup>3</sup> sodium hypophosphite monohydrate; <sup>4</sup> polyacrylic acid with MW = 40,000 with 35% in solids; <sup>5</sup> pentaerythrole; <sup>6</sup> polyacrylic acid of MW = 60,000; 20% neutralized with sodium hydroxide; with 26.3% in salids;<sup>7</sup> 29.6 grams of epoxy-functional silane (1% active) were also added; <sup>8</sup> polyacrylic acid of MW = 60,000; 40% neutralized with sodium hydroxide; with 27.5% in salids;<sup>9 </sup>29.9 grams of epoxy-functional silane (1% active) were added as well; 10 a copolymer of 57 parts of acrylic acid and 25.7 parts of maleic acid prepared in the presence of 17.3 parts of sodium hypophosphite (45% in salts)
Samples 2-5 of this invention were prepared. Comparison A contains a polyacid, but not
ES 2 109 441 T5 contains a polyol or an accelerator containing phosphorus. Comparison B was neutralized to a greater degree than about 30% with a fixed base.
Example 3
Treatment of heat resistant nonwovens and tension test of treated nonwovens
A fiberglass nonwoven substrate was prepared on a Fourdriner slant wire pilot line (typical fiberglass mat forming machine). Fiberglass 3.2 cm long (Owens Corning Fiberglas 685-M fiber) was used. The glass fiber was dispersed with 14 ppm of cationic dispersant (KATAPOL VP<sup>TM</sup>-532; GAF Chemical Corp.) and 31 ppm polyacrylamide thickener (Nalco<sup>TM</sup> 2386). The weight of the prepared mat base was 0.08 kgm<sup>-2</sup>. In the laboratory, the continuous sheet was cut into 17.8 cm by 27.9 cm sheets, which were placed in a 600 muffle furnace.<sup>°</sup>C to burn off any binder and residual organic materials. Sample 1, to which 0.5% by weight (weight based on the weight of the binder solids) of epoxy-functional aminosilane had been added, was then applied to the amino, the excess binder was removed by vacuum and The treated lamin was dried and curd in a Mathis oven for 3 minutes at 200<sup>°</sup>C. The binder add-on was 28% (weight of dry binder based on weight of glass).
The cured lamina was then cut into 2.54 by 10.16 cm strips. The strips were tested for tensile strength by placing them in the jaws of a Thwing-Albert Intelect 500 tension tester. The samples were drawn at a head speed of 2 inches per minute. Wet stress resistance was measured by soaking a second series of identically prepared cured strips of lamin. The samples were soaked in water at 85<sup>°</sup>C for 1 hour. The samples were removed from the water and immediately tested for tensile strength while still wet.
The tensile strength of a nonwoven fabric treated with an aqueous curable composition which is a significant fraction of the dry tensile strength of a similarly treated nonwoven fabric is taken here as an indicator that the composition has cured. and results in useful high temperature performance of the nonwoven fabric treated with the curable aqueous composition.
Test results for samples 1-5 and AB comparisons were obtained as above, except that sample 3 was applied to a microglass substrate (Whatman 934-AH) and are presented in table 3.1.
TABLE 3.1
Tensile strength of treated nonwovens
<td>Show</td><td>Tensile strength<sup>*</sup> dry (lb./in.)</td><td>Tensile Strength * Wet (lb./in.)</td>
<td> 1</td><td> 35</td><td> 20</td>
<td> 2</td><td> 25,8</td><td> 21,1</td>
<td> 3</td><td> 13,2</td><td> 9,2</td>
<td> 4</td><td> 28,0</td><td> 18,2</td>
<td> 5</td><td> 26</td><td> 13,2</td>
<td>Friend</td><td> 30,2</td><td> 2,0</td>
<td>Comp.B</td><td> 29,5</td><td> 4,7</td>
* expressed as: x 5.5 kgcm <sup>1</sup> (based on the calculation that 1 lb / in is equivalent to 0.18kgcm<sup>-1</sup>).
Example 4
Effect of the accelerator level on the performance of fiberglass nonwovens treated with aqueous curable composition
Samples 6-9 and Comparison C were prepared as follows. To a mixture of 100 grams of polyacrylic acid (neutralized to a degree of 3% with a fixed base) and 25.6 grams of glycerol were added
ES 2 109 441 T5 various amounts of sodium hypophosphite monohydrate (SHP) as indicated in table 4.1. These aqueous compositions were applied to a microglass substrate (Whatman 934-AH) and analyzed following the procedure of Example 3. The results are presented in Table 4.1.
TABLE 4.1
Throttle level effect
<td rowspan="2">Show</td><td rowspan="2">wt% SHP</td><td colspan="2">Tensile Strength * (lb./in.)</td>
<td>dry</td><td>wet</td>
<td> 6</td><td> 12,5</td><td> 13,9</td><td> 11,4</td>
<td> 7</td><td> 8,3</td><td> 16,1</td><td> 11,7</td>
<td> 8</td><td> 4,2</td><td> 12,8</td><td> 10,5</td>
<td> 9</td><td> 2,1</td><td> 16,4</td><td> 8,5</td>
<td>Comp.C</td><td> 0</td><td> 13,1</td><td> 0,5</td>
* expressed as: x 5.5 kgcm <sup>1</sup> (based on the calculation that 1 lb / in is equivalent to 0.18 kgcm<sup>-1</sup>).
Samples 6-9 of this invention show significant preservation of tensile strength in the wet tensile strength test. Comparison C, which contains a polyacid and a polyol, but does not contain a phosphorous-containing accelerator, shows basically no wet tensile strength.
Example 5
Effect of the accelerator composition on the performance of fiberglass nonwovens treated with the curable aqueous composition
To a mixture of 168.6 grams of polyacrylic acid (with 25% in salts; neutralized to 3% with a fixed base) and 23.5 g of bis- [N, N-di (e-hydroxyethyl) adipamide (with 40% in solids) 4.32 g of various accelerators were added as indicated in table 5.1. These aqueous compositions were applied to glass fiber nonwovens and analyzed following the procedure of Example 3. The results are presented in Table 5.1.
TABLE 5.1
Throttle composition effect
<td rowspan="2">Show</td><td rowspan="2">Throttle</td><td colspan="2">Tensile Strength * (lb./in.)</td>
<td>dry</td><td>wet</td>
<td> 10</td><td>sodium hypophosphite</td><td> 32,7</td><td> 22,7</td>
<td> 11</td><td>phosphate acid</td><td> 36,4</td><td> 9,7</td>
<td> 12</td><td>phosphorous acid</td><td> 35,4</td><td> 20,6</td>
<td> 13</td><td>sodium dihydrogen phosphate</td><td> 39,1</td><td> 16,5</td>
<td>Comp.D</td><td>p-toluenesulfáonic acid</td><td> 42,5</td><td> 0,8</td>
<td>Comp. AND</td><td>disoadic hydrogen phosphate</td><td> 33,1</td><td> 0,3</td>
<sup>*</sup> expressed as: x 5.5 kgcm<sup>-1</sup> (based on the calculation that 1 lb / in is equivalent to 0.18 kgcm<sup>-1</sup>).
IS 2 109 441 T5
Example 6
Effect of the amount of neutralization on the performance of glass fiber nonwovens treated with a curable aqueous composition that contains a reactive polyol and does not contain an accelerator
A mixture of 100 grams of polyacrylic acid (MW = 60,000; with 25% solids), which had been neutralized to 2% with a fixed base during polyacid synthesis, and 41.7 g of bis- [N, N-di (ehydroxyethyl) adipamide (with 40% solids) was adjusted to different degrees of neutralization (calculated as neutralized acid equivalents relative to total acid equivalents) with sodium hydroxide, a fixed base, as indicated in Table 6.1. These aqueous compositions were applied to glass fiber nonwovens and analyzed according to the procedure of Example 3. The results are presented in Table 6.1.
TABLE 6.1
Effect of the degree of neutralization
<td rowspan="2">Show</td><td rowspan="2">% neutralization</td><td colspan="2">Tensile Strength * (lb./in.)</td>
<td>dry</td><td>wet</td>
<td> 14</td><td> 2</td><td> 36</td><td> 19</td>
<td> 15</td><td> 12</td><td> 37</td><td> 15</td>
<td> 16</td><td> 22</td><td> 38</td><td> 10</td>
<td> 17</td><td> 32</td><td> 39</td><td> 5</td>
<td>Comp.F</td><td> 42</td><td> 38</td><td> 1</td>
<td>Comp.G</td><td> 52</td><td> 34</td><td> 0</td>
<sup>*</sup> expressed as: x 5.5 kgcm<sup>-1</sup> (based on the calculation that 1 lb / in is equivalent to 0.18 kgcm<sup>-1</sup>).
Samples 14-17 of this invention incorporating a reactive polyol show a higher level of conservation of wet tensile strength, while comparison F and comparison G do not do so at higher degrees of neutralization.
Example 7
Effect of the degree of neutralization on the performance of fiberglass nonwovens treated with curable aqueous composition
To a mixture of 100 grams of polyacrylic acid (PM = 60,000; with 25% in solids), which had been neutralized to 2% with a fixed base during the synthesis of the polyacid, and 41.7 g of bis- [N, Ndi (e-hydroxyethyl) adipamide, 4.17 g of Sodium hypophosphite monohydrate and the composition was regulated to different degrees of neutralization (calculated as neutralized acid equivalents relative to total acid equivalents) with sodium hydroxide, a fixed base, as indicated in Table 7.1. These aqueous compositions were applied to glass fiber nonwovens and analyzed according to the procedure of Example 3. The results are presented in Table 7.1.
IS 2 109 441 T5
TABLE 7.1
Effect of the degree of neutralization
<td rowspan="2">Show</td><td rowspan="2">% neutralization</td><td colspan="2">Tensile Strength * (lb./in.)</td>
<td>dry</td><td>wet</td>
<td> 18</td><td> 2</td><td> 29,8</td><td> 19,9</td>
<td> 19</td><td> 12</td><td> 32,1</td><td> 18,1</td>
<td> 20</td><td> 22</td><td> 28,0</td><td> 18,2</td>
<td> 21</td><td> 32</td><td> 26,8</td><td> 11,2</td>
<td>Comp.H</td><td> 42</td><td> 29,5</td><td> 4,7</td>
<td>Comp.I</td><td> 52</td><td> 28,9</td><td> 5,1</td>
* expressed as: x 5.5 kgcm <sup>1</sup> (based on the calculation that 1 lb / in is equivalent to 0.18 kgcm<sup>-1</sup> ).
Samples 18-21 of this invention show a high level of conservation of tensile strength in the wet, while comparison H and comparison I do not do so at higher degrees of neutralization.
Example 8
Effect of heating time / temperature on the performance of glass fiber nonwovens treated with curable aqueous composition
At a mixture of 100 grams of polyacrylic acid (MW = 60,000; with 25% in solids, which had been neutralized to 3% with a fixed base) and 41.7 g of bis- [N, N-di (e -hydroxyethyl) adipamide (with 40% solids) 4.17 g of sodium hypophosphite monohydrate were added. This aqueous composition was applied to fiberglass nonwovens and analyzed according to the procedure of Example 3. The results are presented in Table 8.1.
TABLE 8.1
Effect of heating time / temperature
<td rowspan="2">Temperature (◦ ')</td><td rowspan="2">Time (min)</td><td colspan="2">Tensile strength (lb./in.)</td>
<td>dry</td><td>wet</td>
<td> 140</td><td> 1</td><td> 30,4</td><td> 0</td>
<td> 140</td><td> 2</td><td> 32,5</td><td> 1,5</td>
<td> 140</td><td> 3</td><td> 35,0</td><td> 1,5</td>
<td> 140</td><td> 4</td><td> 43,4</td><td> 1,5</td>
<td> 160</td><td> 1</td><td> 30,8</td><td> 1,2</td>
<td> 160</td><td> 2</td><td> 36,3</td><td> 8,5</td>
<td> 160</td><td> 3</td><td> 44,6</td><td> 19,6</td>
<td> 160</td><td> 4</td><td> 40,8</td><td> 23,9</td>
<td> 180</td><td> 1</td><td> 43,3</td><td> 10,9</td>
<td> 180</td><td> 2</td><td> 37,5</td><td> 25,7</td>
<td> 180</td><td> 3</td><td> 32,9</td><td> 23,9</td>
<td> 180</td><td> 4</td><td> 32,5</td><td> 21,5</td>
<td> 200</td><td> 1</td><td> 35,6</td><td> 18,1</td>
<td> 200</td><td> 2</td><td> 28,3</td><td> 18,4</td>
<td> 200</td><td> 3</td><td> 30,0</td><td> 20,1</td>
<td> 200</td><td> 4</td><td> 27,4</td><td> 19,0</td>
<sup>*</sup> expressed as: x 5.5 kgcm<sup>-1</sup> (based on the calculation that 1 lb / in is equivalent to 0.18 kgcm<sup>-1</sup>).
IS 2 109 441 T5
The samples of this invention exhibit a high level of preservation of wet tensile strength when sufficient heat treatment is applied for a sufficient time. Warming up to 140<sup>°</sup>C for a period of time longer than 4 minutes is believed effective for curing the composition. Temperatures above about 150 are preferred<sup>°</sup>C up to 200<sup>°</sup>C. Example 9
Use of sodium hypophosphite as an accelerator component of the curable aqueous composition
Preparation and analysis of sample 22. A mixture of 19.0 g of polyacrylic acid of MW = 60,000 (25% in solids), 0.475 g of sodium hypophosphite monohydrate, 2.023 g of glycerol and 2.662 g of water was mixed thoroughly. and poured into a flat Petri dish; The mixture was air dried for 4-5 days and then placed in a forced draft oven for 8 hours at 35<sup>°</sup>C. The resulting film was about 0.1 cm thick. A sample weighing approximately 0.5 g was cut from the film, heated as indicated in Table 9.1, and reweighed. The cured film was then soaked in water for 48 hours and weighed. The gravimetric ratio of swelling was determined using a correction for the soluble fraction. The procedure was independently found to have a 95% confidence interval of 0.60. The swelling ratio is taken as a measure of the degree of cure, the lower numbers indicating a higher crosslinking density and, therefore, a higher degree of cure and greater efficiency as a polymeric binder for heat resistant nonwovens.
Preparation and analysis of comparison J. A mixture of 20.0 g of polyacrylic acid of MW = 60,000 (25% in solids) and 2.13 g of glycerol was mixed thoroughly and poured into a flat Petri dish; The mixture was air dried for 4-5 days and then placed in a forced draft oven for 8 hours at 35<sup>°</sup>C. The resulting film was treated and the swelling ratio was measured as in the analysis of sample 22 described above.
TABLE 9.1
Effect of the accelerator on the swelling ratio of the curable aqueous composition
<td rowspan="2">Show</td><td colspan="2">Reason for swelling</td>
<td>(heated 6 min. to 150<sup>°</sup>C)</td><td>(heated 6 min. at 180 ° C)</td>
<td> 23</td><td> 10,4</td><td> 4,5</td>
<td>Comp. J</td><td> 16,5</td><td> 7,1</td>
Sample 23 of this invention incorporating an accelerator containing phosphorous exhibits a superior cure response than comparison J, which does not contain an accelerator.
Example 10
Use of sodium hypophosphite as an accelerating component of the curable aqueous composition using various polyols
Preparation of samples 24-28 and KO comparison samples. A mixture of polyacrylic acid of MW = 60,000 (PAA in 25% in solids), sodium hypophosphite monohydrate (SHP), polyol and water, as indicated in table 10.1, was mixed thoroughly and poured into a flat Petri dish. ; The sample was treated and analyzed as in Example 9. The swelling ratios are presented in Table 10.2.
IS 2 109 441 T5
TABLE 10.1
Preparation of samples 24-28 and KO comparison samples
<td>Show</td><td>g PAA</td><td>g SHP</td><td>g polyol</td><td>g water</td>
<td> 24</td><td> 16,0</td><td> 0,40</td><td>2.95 diethylene glycol</td><td> 5,14</td>
<td>Comp.K</td><td> 16,0</td><td> 0</td><td>2.95 diethylene glycol</td><td> 0</td>
<td> 25</td><td> 16,0</td><td> 0,475</td><td>2.05 ethylene glycol</td><td> 2,72</td>
<td>Comp.L</td><td> 16,0</td><td> 0</td><td>2.05 ethylene glycol</td><td> 0</td>
<td> 26</td><td> 19,0</td><td> 0,475</td><td>2.84 D-glucoanic acid<sup>1</sup></td><td> 9,56</td>
<td>Comp.M</td><td> 19,0</td><td> 0</td><td>2.84 D-glucaonic acid<sup>1</sup></td><td> 9,56</td>
<td> 27</td><td> 19,0</td><td> 0,475</td><td>2.82 β-D-lactose</td><td> 4,52</td>
<td>Comp.N</td><td> 19,0</td><td> 0</td><td>2.82 β-D-lactose</td><td> 4,52</td>
<td> 28</td><td> 19,0</td><td> 0,475</td><td>2.82 sucrose</td><td> 4,52</td>
<td>Comp.O</td><td> 19,0</td><td> 0</td><td>2.82 sucrose</td><td> 4,52</td>
<sup>1</sup> Added as a calcium salt.
TABLE 10.2
Effect of the accelerator on the swelling ratio of curable aqueous compositions
<td>Show</td><td>Swelling root (heated 6 min. At 180 ° C)</td>
<td> 24</td><td> 4,0</td>
<td>Comp. K</td><td> 8,3</td>
<td> 25</td><td> 3,5</td>
<td>Comp. L</td><td> 5,5</td>
<td> 26</td><td> 14,4</td>
<td>Comp. M</td><td>dissolved</td>
<td> 27</td><td> 9,6</td>
<td>Comp. N</td><td>dissolved</td>
<td> 28</td><td> 7,6</td>
<td>Comp. OR</td><td>dissolved</td>
Samples 24-28 of this invention incorporating various polyols and a phosphorous-containing accelerator exhibit superior cure response than KO comparisons that do not contain accelerator.
Example 11
Effect of polyol component level on curable aqueous composition in curing
Preparation of samples 29-36. A mixture of polyacrylic acid with MW = 60,000 (PAA in 25% in salts), sodium hypophosphite monohydrate (SHP) and polyol, as indicated in table 11.1, is mixed thoroughly and poured into a flat Petri dish; the sample will be treated and analyzed following example 9. The swelling ratios are presented in table 11.2.
IS 2 109 441 T5
TABLE 11.1
Sample preparation 29-36
<td>Show</td><td>g PAA</td><td>g SHP</td><td>g polyol</td>
<td> 29</td><td> 22,0</td><td> 0,55</td><td>0.235 glycerol</td>
<td> 30</td><td> 20,0</td><td> 0,50</td><td>0.534 glycerol</td>
<td> 31</td><td> 20,0</td><td> 0,50</td><td>1,065 glycerol</td>
<td> 32</td><td> 19,0</td><td> 0,475</td><td>2,023 glycerol</td>
<td> 33</td><td> 21,0</td><td> 0,525</td><td>1.46 pVOH<sup>1</sup></td>
<td> 34</td><td> 19,0</td><td> 0,475</td><td>3.30 pVOH</td>
<td> 35</td><td> 16,5</td><td> 0,413</td><td>5.73 pVOH</td>
<td> 36</td><td> 14,0</td><td> 0,35</td><td>9.72 pVOH</td>
<sup>1</sup> pVOH - the polyvinyl alcohol used was a solution with 25% solids content of Airvol 203.
TABLE 11.2.
Effect of polyol level on swelling ratio of curable aqueous compositions
<td>Show</td><td>Relationship hydroxyl / carboxyl</td><td>Swelling ratio (heated 6 min. At 180 ° C)</td>
<td> 29</td><td> 0,1</td><td> 9,9</td>
<td> 30</td><td> 0,25</td><td> 5,4</td>
<td> 31</td><td> 0,5</td><td> 7,0</td>
<td> 32</td><td> 1,0</td><td> 4,5</td>
<td> 33</td><td> 0,1</td><td> 14,0</td>
<td> 34</td><td> 0,25</td><td> 6,8</td>
<td> 35</td><td> 0,5</td><td> 4,4</td>
<td> 36</td><td> 1,0</td><td> 4,5</td>
Samples 29-32 and 33-36, all according to the present invention, which incorporate different polyols and an accelerator with phosphorus content present a response to curing that increases in a general way, that is, a decreasing swelling ratio, with the increased hydroxyl / carboxyl ratio. Example 12
Use of Various Accelerators Containing Phosphorus in Curable Aqueous Compositions
Preparation of samples 37-40 and comparison sample P. A mixture of polyacrylic acid with MW = 60,000 (PAA in 25% in solids), accelerator, glycerol and water, as indicated in table 12.1, was mixed to bottom and poured into a flat Petri dish; The sample was treated and analyzed according to Example 9. The swelling ratios are presented in Table 12.2.
IS 2 109 441 T5
TABLE 12.1
Preparation of samples 37-40 and comparison sample P
<td>Show</td><td>g PAA</td><td>g throttle</td><td>g glycerol</td><td>g water</td>
<td> 37</td><td> 23,0</td><td>0.965 Na4P2O7 .10H2O</td><td> 2,45</td><td> 2,83</td>
<td> 38</td><td> 23,0</td><td>0.676 H3PO4 (85%)</td><td> 2,45</td><td> 3,12</td>
<td> 39</td><td> 23,0</td><td>0.575 H3PO3</td><td> 2,45</td><td> 3,22</td>
<td> 40</td><td> 23,0</td><td>0.723 NaH2PO2H2O</td><td> 2,45</td><td> 3,08</td>
<td>Comp. P</td><td> 20,0</td><td> 0</td><td> 2,13</td><td> 0</td>
TABLE 12.2.
Effect of Accelerator Type on the Swelling Reason of Curable Aqueous Compositions
<td>Show</td><td>Swelling ratio (heated 6 min. At 180 ° C)</td>
<td> 37</td><td> 5,9</td>
<td> 38</td><td> 2,0</td>
<td> 39</td><td> 2,1</td>
<td> 40</td><td> 4,1</td>
<td>Comp.P</td><td> 7,1</td>
Samples 37-40 of this invention incorporating various phosphorous-containing accelerators exhibit superior cure response than comparison sample P, which does not contain an accelerator. Example 13
Use of various polyacid components in curable aqueous compositions
Sample preparation 41-44. A mixture of polyacid, as indicated in Table 13.1, sodium phosphite monohydrate (SHP) accelerator, glycerol and water will be mixed thoroughly and poured into a flat Petri dish; The sample will be treated and analyzed as in Example 9. The swelling ratios are presented in Table 13.2; swelling ratios were determined using the indicated solvents, but not in water.
TABLE 13.1
Sample preparation 41-44
<td>Show</td><td>g polioacid</td><td>g SHP</td><td>g glycerol</td><td>g water</td>
<td> 41</td><td>17.0 A</td><td> 0,25</td><td> 0,51</td><td> 6,79</td>
<td> 42</td><td>17.0 B</td><td> 0,25</td><td> 0,53</td><td> 7,28</td>
<td> 43</td><td>17.0 C</td><td> 0,25</td><td> 0,52</td><td> 7,09</td>
<td> 44</td><td>18.0 D</td><td> 0,19</td><td> 0,67</td><td> 5,01</td>
Polyacid A = 70 styrene / 15 methyl methacrylate / 15 acrylic acid (25% in solids)
Polyacid B = 50 styrene / 10 hydroxyethyl methacrylate / 10 methyl methacrylate / 30 acrylic acid (25% in solids) Polyacid C = 60 styrene / 10 a-methylstyrene / 30 acrylic acid (25% in solids)
Polyacid D = 70 2-ethylhexyl acrylate / 30 methacrylic acid (35% in salts)
IS 2 109 441 T5
TABLE 13.2
Effect of Polyacid Type on Swelling Ratio of Curable Aqueous Compositions
<td>Show</td><td>Swelling ratio (heated 6 min. At 180 ° C)</td>
<td> 41</td><td>8.5 (methyl ethyl ketone)</td>
<td> 42</td><td>5.1 (methyl ethyl ketone)</td>
<td> 43</td><td>7.6 (methyl ethyl ketone)</td>
<td> 44</td><td>5.2 (acetone)</td>
Samples 41-44 of this invention incorporating various polyacids exhibit cure response. All polyacid compositions alone and not as part of the curable composition were dissolved in the solvents used.
Example 14
Use of Polyacrylic Acid Components of Various Molecular Weights in Curable Aqueous Compositions
Sample preparation 45-50. A mixture of polyacrylic acid (PAA), as indicated in table 14.1, sodium hypophosphite monohydrate (SHP) accelerator, polyol, as indicated in table 14.1 and water was mixed thoroughly and poured into a flat Petri dish; The sample was treated and analyzed as in Example 9. The swelling ratios are presented in Table 14.2.
TABLE 14.1
Preparation of samples 45-50
<td>Show</td><td>gPAA</td><td>gSHP</td><td>g polyol</td>
<td> 45</td><td>14.0 (MW = 2000; 40% solids)</td><td> 0,56</td><td>2.39 glycerol</td>
<td> 46</td><td>19.0 (MW = 60,000; 25% solids)</td><td> 0,475</td><td>2.02 glycerol</td>
<td> 47</td><td>19.0 (MW = 190,000; 25% solids)</td><td> 0,475</td><td>2.02 glycerol</td>
<td> 48</td><td>16.0 (MW = 2000; 40% solids)</td><td> 0,64</td><td>4.45 pVOH</td>
<td> 49</td><td>24.0 (PM = 60,000; 25% solid)</td><td> 0,60</td><td>4.17 pVOH</td>
<td> 50</td><td>24.0 (MW = 190,000; 25% solids)</td><td> 0,60</td><td>4.17 pVOH</td>
IS 2 109 441 T5
TABLE 14.2
Effect of Polyacrylic Acid Molecular Weight on Swelling Ratio of Curable Aqueous Compositions
Sample Ratio Hydroxyl / carboxyl swelling ratio (6 min. (6 min. At 150 ° C) 180 ° C)
<td> 45</td><td> 1,0</td><td>dissolved</td><td> 14,1</td>
<td> 46</td><td> 1,0</td><td> 10,4</td><td> 4,5</td>
<td> 47</td><td> 1,0</td><td> 8,7</td><td> 4,9</td>
<td> 48</td><td> 0,25</td><td>dissolved</td><td> 23,4</td>
<td> 49</td><td> 0,25</td><td> 17,6</td><td> 9,4</td>
<td> 50</td><td> 0,25</td><td> 7,7</td><td> 4,4</td>
Samples 45-50 of this invention incorporating polyacrylic acid of various molecular weights show curing response. Higher molecular weight polyacrylic acid and higher temperature heat treatment favor a better cure response.
Example 15
Use of acids of polyacid components formed in the presence of sodium hypophosphite in curable aqueous compositions
Preparation of samples 51 and comparison sample Q. A mixture of poly (66 acrylic / 28 maleic anhydride) (polyacid; 56% in solids) that was prepared in the presence of 6% by weight of sodium hypophosphite monohydrate, where glycerol was used. indicated in Table 15.1 and water was mixed thoroughly and poured into a flat Petri dish; The sample was treated and analyzed as in Example 9. The swelling ratios are presented in Table 15.2.
Preparation of samples 52 and comparison sample R. A mixture of poly (82 acrylic / 12 maleic anhydride) (polyacid; 56% in solids) that was prepared in the presence of 6% by weight of sodium hypophosphite monohydrate, glycerol where indicated in Table 15.1 and water was mixed thoroughly and poured into a flat Petri dish; The sample was treated and analyzed as in Example 9. The swelling ratios are presented in Table 15.2.
TABLE 15.1
Preparation of samples 51-52 and comparison samples QR
<td>Show</td><td>g polioacid</td><td>g water</td><td>g polyol</td>
<td> 51</td><td> 13,0</td><td> 18,56</td><td>3.13 glycerol</td>
<td>Comp. Q</td><td> 13,0</td><td> 18,56</td><td> 0</td>
<td> 52</td><td> 13,0</td><td> 18,42</td><td>3.02 glycerol</td>
<td>Comp. R</td><td> 13,0</td><td> 18,42</td><td> 0</td>
IS 2 109 441 T5
TABLE 15.2.
Effect of Polyacid Components Formed in the Presence of Sodium Hypophosphite on the Swelling Ratio of Curable Aqueous Compositions
<td>Show</td><td>Swelling root (heated 6 min. At 180 ° C)</td>
<td> 51</td><td> 5,4</td>
<td>Comp. Q</td><td>dissolved</td>
<td> 52</td><td> 11,3</td>
<td>Comp. R</td><td>dissolved</td>
Samples 51-52 of this invention incorporating polyacid components formed in the presence of sodium hypophosphite exhibit a cure response. The QR comparison samples show that the corresponding polyacid components formed in the presence of sodium hypophosphite do not cure in the absence of a polyol under the applied conditions.
Example 16
Use of Various Hydroxylamines as Polyol Component in Curable Aqueous Compositions
Preparation of samples 53-57. A mixture of polyacrylic acid (45% solids content) of MW = 10 000 with its carboxylic acid groups neutralized to a degree of 1.9% with sodium hydroxide (fixed base) and to an additional degree of 5.3 % with ammonium hydroxide (volatile base) at pH =
3.5, sodium hypophosphite monohydrate accelerator (3.3% solution), polyolol and water, as indicated in table 16.1, the amount chosen to give a total level of solids of approximately 18% is mixed thoroughly and apply to a sheet of fiberglass formed in the wet follow the procedure of the example
3. The results of tensile strength are presented in table 16.2. Furthermore, the samples were also analyzed at a lower temperature. The results of tensile strength are presented in table 16.3.
TABLE 16.1
Preparation of samples 53-57
<td>Show</td><td>g PAA</td><td>g throttle</td><td>g polyol</td><td>g water</td>
<td> 53</td><td> 104,6</td><td> 2,1</td><td>6.1 P1</td><td> 187,2</td>
<td> 54</td><td> 107,2</td><td> 2,1</td><td>4.6 P2</td><td> 186,1</td>
<td> 55</td><td> 102,5</td><td> 2,1</td><td>6.3 P3</td><td> 189,1</td>
<td> 56</td><td> 108,3</td><td> 2,1</td><td>4.1 P4</td><td> 185,5</td>
<td> 57</td><td> 103,6</td><td> 2,1</td><td>4.7 P5</td><td> 189,7</td>
<sup>1</sup> The polyols are: P1 = diisopropanolamine; P2 = 2- (2-aminoethyl) ethanol; P3 = triethanolamine; P4 = tris (hydroxymethyl) aminomethane; P5 = diethanolamine.
IS 2 109 441 T5
TABLE 16.2.
Tension Test Results of Treated Nonwovens Heated to 200<sup>°</sup>C
<td>Show</td><td>Dry tensile strength<sup>* </sup>(lb./in.)</td><td>Wet Tensile Strength * (lb./in.)</td>
<td> 53</td><td> 41,0</td><td> 29,2</td>
<td> 54</td><td> 41,5</td><td> 28,5</td>
<td> 55</td><td> 47,8</td><td> 28,5</td>
<td> 56</td><td> 42,0</td><td> 21,7</td>
<td> 57</td><td> 41,2</td><td> 28,9</td>
<sup>*</sup> expressed as: x 5.5 kgcm<sup>-1</sup> (based on the calculation that 1 lb / in is equivalent to 0.18 kgcm<sup>-1</sup>).
TABLE 16.3.
Tensioon Test Results of Treated Nonwovens Heated to Different Temperatures
Tensile strength<sup>*</sup>
<td colspan="3">Show</td><td rowspan="2">dry 190C</td><td colspan="2">(lb./in.)</td><td colspan="3">wet</td>
<td></td><td>170C</td><td>180C</td><td>200C</td><td>170C</td><td>180C</td><td>190C</td><td>200C</td>
<td> 53</td><td><sub>-</sub></td><td> 44,7</td><td> 46,2</td><td> 41,0</td><td> 3,5</td><td> 18,6</td><td> 23,0</td><td> 29,2</td>
<td> 54</td><td> -</td><td> 55,0</td><td> -</td><td> -</td><td> -</td><td> 16,7</td><td> -</td><td> 28,5</td>
<td> 55</td><td> 39,2</td><td> 46,7</td><td> -</td><td> 47,8</td><td> 4,2</td><td> 19,3</td><td> -</td><td> 31,5</td>
<td> 56</td><td> -</td><td> 41,1</td><td> -</td><td> 42,0</td><td> -</td><td> 5,1</td><td> -</td><td> 21,7</td>
<td> 57</td><td> 43,8</td><td> 48,6</td><td><sub>-</sub></td><td> 41,2</td><td> 4,0</td><td> 14,3</td><td><sub>-</sub></td><td> 28,9</td>
<sup>*</sup> expressed as: x 5.5 kgcm<sup>-1</sup> (based on the calculation that 1 lb / in is equivalent to 0.18 kgcm<sup>-1</sup> .
Samples 53-57 of this invention incorporating a hydroxylamine as a polyol component provide a useful level of tensile strength.
Example 17
Use of a diamine instead of the polyol component
Sample preparation 58. A mixture of 101.1 g of polyacrylic acid (45% in total solids) of PM = 10,000 with their carboxylic acid groups neutralized to a degree of 1.9% with sodium hydroxide (fixed base) and to an additional degree of 5.3% with ammonium hydroxide (volatil base) at pH = 3, 5, 2.1 g of sodium hypophosphite monohydrate accelerator (3.3% solution), 7.4 g of hexanediamine and 189.4 g of water was mixed thoroughly and applied to a glass fiber sheet formed into wet following the procedure of example 3. This lamin, after making a vacuum to remove excess binder composition, was heated for three minutes at 200<sup>°</sup>C; The sample was analyzed as in Example 3. The dry tensile strength was 8.8 kgcm<sup>-1</sup> and a wet tensile strength of 3.52 kgcm<sup>-1</sup>.
Example 18
Use of triethanolamine as a polyol component with phosphatinated-terminated polyacrylic acid
Preparation of sample 59. A mixture of 87.5 g of polyacrylic acid terminated in phosphatinated groups prepared following the procedure of sample 51 (at 53.1% solids content) of MW =
IS 2 109 441 T5
3500 With its carboxylic acid groups neutralized to a degree of 1.0% with sodium hydroxide (fixed base), 14.2 g of triethanolamine and 198.3 g of water, it was thoroughly mixed and applied to a fiber lining of Glass formed wet following the procedure of Example 3, except that the fiberglass was 1.91 cm long. This sheet, after being subjected to a vacuum to remove the excess binder composition, was heated for three minutes at 200<sup>°</sup>C; The sample was analyzed as in Example 3. The dry tensile strength was 6.39 kgcm<sup>-1</sup> and the tensiíííon resistance in wet of 4.41 kgcm<sup>-1</sup> .
Contents34
43 members in 24 offices
Priority claims10
| Document | Office | Kind | Date |
|---|---|---|---|
| 19920926262 | United States of America | – | |
| 92626292 | United States of America | A | |
| 92626292 | United States of America | A | |
| 19930075715 | United States of America | – | |
| 7571593 | United States of America | A | |
| 7571593 | United States of America | A | |
| 75715 | – | – | – |
| 93305665 | – | – | – |
| US19920926262 | – | – | – |
| US19930075715 | – | – | – |
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| EP0583086A1 | European Patent Office (EPO) | A1 | |
| KR940004005A | Republic of Korea | A | |
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| AT160597T | Austria | T | |
| ATE160597T1 | Austria | T1 | |
| DE69315393D1 | Germany | D1 | |
| ES2109441T3 | Spain | T3 | |
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| EP0583086B2 | European Patent Office (EPO) | B2 | |
| DE69315393T3 | Germany | T3 | |
| ES2109441T5This record | Spain | T5 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Definitive protectionFG2A | FG2A |
Numbers
- Publication
- 2109441
- Publication, DOCDB
- 2109441
- Publication, EPODOC
- ES2109441T
- Application
- 93305665
- Application, DOCDB
- 93305665
- Application, EPODOC
- ES19930305665T
Titles2
- Spanish
- COMPOSICION ACUOSA CURABLE Y SU USO COMO AGLUTINANTE DE NO TEJIDOS DE FIBRAS DE VIDRIO
- English
- CURABLE AQUEOUS COMPOSITIONS AND THEIR USE AS A BINDER OF FIBERGLASS NON-FABRIC GENERATIONS.
Classification
- CPC, 4
- C08F8/14
- C08L67/00
- D04H1/587
- D04H1/64
- IPC, 14
- C08G63 12
- C08F8 14
- C09J167 00
- C09J167 02
- D04H1 64
- D06M13 02
- D06M13 148
- D06M13 184
- D06M13 192
- D06M13 322
- D06M13 368
- D06M13 402
- D06M13 405
- D06M101 00