WO1992009660A1

WO1992009660A1 - Low viscosity high strength acid binder

Info

Publication number: WO1992009660A1
Application number: PCT/US1991/008692
Authority: WO
Inventors: Paul J. Steinwand
Original assignee: Union Oil Company Of California
Priority date: 1990-11-30
Filing date: 1991-11-20
Publication date: 1992-06-11
Also published as: AU1238292A

Abstract

A low viscosity, fast-curing binder for textile substrates is produced by admixing an aqueous emulsion copolymer latex with an aqueous solution copolymer formed by the copolymerization of an olefinically unsaturated polycarboxylic acid, an olefinically unsaturated monocarboxylic acid, and an olefinically unsaturated carboxylic acid hydroxy ester. Viscosities in the range of about 2 cps at 25 % total solids to about 1000 cps at 35 % total solids are realized by using solution copolymers containing about 40 %-60 % by weight of polycarboxylic acid.

Description

LOW VISCOSITY HIGH STRENGTH ACID BINDER

FIELD OF THE INVENTION

This invention relates to binders for textile materials. In one of its more particular aspects this invention relates to polymeric binders having the properties of low viscosity and high strength.

BACKGROUND OF THE INVENTION

During the past few years there has been a substantial growth in the production of high-strength textile materials, especially paper and cloth products having a nonwoven, randomly-oriented structure, bonded with a polymeric resin binder. Such products are finding wide use as high-strength, high-absorbency materials for disposable items such as consumer and industrial wipes or towels, diapers, surgical packs and gowns, industrial work clothing and feminine hygiene products. They are also used for durable products such as carpet and rug backings, apparel interlinings, automotive components and home furnishings, and for civil engineering materials such as road underlays. There are several ways to apply a binder to these materials, including spraying, print binding, and foam application. Further, depending on the end use, various ingredients such as catalysts, cross-linkers, surfactants, thickeners, dyes, and flame retardant salts may also be incorporated into the binder. In the high-speed, high-volume manufacture of cellulosic products such as wet wipes, an important binder property is a fast cure rate; that is, the finished product must reach substantially full tensile strength in a very short time after binder application so that production rates are not unduly slowed down. In these products, such a property is usually obtained either by using a binder which is self-cross-linkable or by incorporating an external cross-linker into the binder formulation. The cross-linker or self-cross-linkable binder apparently not only interacts with reactive groups in the binder, but with the hydroxyl groups on the cellulose fibers as well, to quickly form very strong bonds.

As the need for stronger nonwovens developed, a variety of cross-linking agents for the base binders was utilized. N-methylolacrylamide and other similar cross-linkers were incorporated into the binders. While the strength of the nonwovens increased desirably, it was discovered that many of these cross-linking agents, especially N-methylolacrylamide, emitted formaldehyde during use. The toxicity of formaldehyde caused users to search for non-formaldehyde-emitting alternatives, that is, so-called "zero" formaldehyde binders. An example of a non-formaldehyde-emitting cross-linker is methyl acryloamidoglycolate methyl ether (MAGME). However, while MAGME improved the strength of many copolymeric binders and did not emit formaldehyde, the need for further improving the strength, especially the wet strength, of many copolymeric binders led to the use of various other techniques for strength improvement.

One method of providing a fast curing, zero formaldehyde binder for nonwoven cellulosic materials utilized a binder comprising a solution copolymer formed by copolymerizing a mixture of two or more water soluble olefinically unsaturated organic comonomers. The solution copolymer was admixed with a non-formaldehyde-emitting latex to produce a final composition which, when cured on nonwoven cellulosic material, achieved about 80 percent of fully cured wet tensile strength in 8 seconds or less and which had essentially no emission of formaldehyde from the finished nonwoven.

SUMMARY OF THE INVENTION

While the use of solution copolymers resulted in providing zero formaldehyde binders which had improved wet strengths and which were capable of fast curing, it was found that certain solution copolymers may raise the viscosity and cause thickening of the binders in which they are incorporated. In certain applications it is desirable to maintain the viscosity of the binder at a relatively low level in order to assure adequate penetration of the binder into the nonwoven substrate and to facilitate handling of the binder. Although the binder viscosity can be lowered by using a lesser quantity of solution copolymer, this approach may result in a binder of reduced wet strength. Accordingly, in order to provide a low viscosity binder without reducing the strength thereof, a method of providing low viscosity binders which does not depend upon the use of lesser quantities of solution copolymers is needed.

In accordance with the present invention, a low viscosity, high strength, fast curing, zero formaldehyde binder for textile materials is provided. The binder comprises an admixture of an aqueous emulsion copolymer latex and an aqueous solution copolymer, which admixture is formulated to contain a very high proportion of carboxyl groups. The emulsion copolymer latex typically is a non-formaldehyde-emitting copolymer such as a carboxylated copolymer of an alkenyl aromatic compound and a conjugated diolefin. The solution copolymer typically comprises the product of copolymerization of a mixture of one or more copolymerizable olefinically unsaturated polycarboxylic acids, one or more copolymerizable olefinically unsaturated monocarboxylic acids, and one or more olefinically unsaturated carboxylic acid hydroxy esters..

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a low viscosity, high strength, fast curing, zero formaldehyde binder for textile materials, especially nonwoven cellulosic materials, a process for preparing the binder, an article of manufacture comprising the binder incorporated into a textile substrate, and a method for producing such article of manufacture. The binder, which contains a very high proportion of carboxyl groups, is formulated by mixing an aqueous emulsion copolymer latex with a solution copolymer.

LATEX

The latex of the present invention typically comprises a conjugated diolefin copolymer containing about 10 to about 95 weight percent of one or more alkenyl aromatic comonomers and about 5 to about 90 weight percent of one or more conjugated diolefin comonomers having 4 to about 8 carbon atoms. These copolymers can be either random or block interpolymers. Illustrative alkenyl aromatic comonomers include, for example, styrene and substituted styrenes such as alpha-methylstyrene, p-methylstyrene, chlorostyrene and methylbromostyrene. Illustrative conjugated diolefin comonomers include, for example, butadiene, isoprene, 1,3-pentadiene, 2-ethylbutadiene, and 4-methyl-1,3-pentadiene. The alkenyl aromatic comonomer is preferably present in a concentration of about 20 to about 80 weight percent, most preferably about 40 to about 70 weight percent. The conjugated diolefin comonomer is preferably present in a concentration of about 20 to about 80 weight percent, most preferably about 30 to about 60 weight percent.

The conjugated diolefin copolymers can contain various other comonomers in addition to the alkenyl aromatic comonomer and the conjugated diolefin comonomer, such as vinyl esters of carboxylic acids, mono-olefins, olefinically unsaturated nitriles, olefinically unsaturated carboxylic acid esters, or olefinically unsaturated carboxylic acids, which are preferred.

In an especially preferred embodiment, itaconic acid is copolymerized with styrene and butadiene. The itaconic acid is typically present in a quantity of about 0.5 percent to about 5 percent by weight of total monomers, the larger quantities being preferred. The olefinically unsaturated carboxylic acid, such as itaconic acid, can be added at the start of the polymerization or continuously throughout the polymerization.

Other latexes than conjugated diolefin copolymer latexes can be used in the present invention in place of the conjugated diolefin copolymer latexes. For example, acrylic latexes, vinyl acrylic latexes, vinyl chloride latexes, vinyl acetate latexes, vinylidene chloride latexes and nitrile latexes can be used if desired.

An especially preferred group of latexes includes non-formaldehyde emitting styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/aerylate, and all-acrylate copolymer latexes. The latexes of the present invention can be prepared by free radical solu tion and emulsion polymerization methods including batch, continuous and semi-continuous procedures. For the purposes of this invention, free radical polymerization methods are intended to include radiation polymerization techniques. Illustrative free-radical polymerization procedures suitable for preparing aqueous polymer emulsions involve gradually adding the monomer or monomers to be polymerized simultaneously to an aqueous reaction medium containing a free radical catalyst at rates proportional to the respective percentage of each comonomer in the finished copolymer. Optionally, copolymers can be obtained by adding one or more comonomers disproportionately throughout the polymerization so that the portions of the polymers formed during the initial polymerization stages have a comonomer composition different from that formed during the intermediate or later stages of the same polymerization. For instance, a styrene-butadiene copolymer can be formed by adding a greater proportion or all of the styrene during the initial polymerization stages with the greater proportion of the butadiene being added later in the polymerization.

Illustrative free-radical catalysts are free radical initiators such as hydrogen peroxide, potassium or ammonium peroxydisulfate, dibenzoyl peroxide, lauroyl peroxide, ditertiarybutyl peroxide, 2,2'-azobisisobutyronitrile, either alone or together with one or more reduc ing components such as sodium bisulfite, sodium metabisulfite, glucose, ascorbic acid or erythorbic acid. Ultraviolet and electron beam polymerization methods suitable for initiating free radical polymerizations are discussed in the Handbook of Pressure-Sensitive Adhesive Technology, D. Satas, Ed., Van Nostrand Reinhold Company, New York (1982), particularly at pages 586-604 and the references cited therein. The foregoing references in their entireties are incorporated herein by reference.

Physical stability of the dispersion usually is achieved by providing in the aqueous reaction medium one or more nonionic, anionic, and/or amphoteric surfactants including copolymerizable surfactants such as sulfonated alkylphenol polyalkyleneoxy maleate, sulfoethyl methacrylate, or alkenyl sulfonates. Illustrative of nonionic surfactants are alkylpolyglycol ethers such as ethoxylation products of lauryl, oleyl, or stearyl alcohols or mixtures of alcohols such as coconut fatty alcohols; alkylphenol polyglycol ethers such as ethoxylation products of octyl- or nonylphenol, diisopropylphenol, triisopropylphenol, or di- or tritertiary butyl phenol. Illustrative of anionic surfactants, for example, are alkali metal or ammonium salts of alkyl, aryl, or alkylaryl sulfonates, sulfates, phosphates or phosphonates. Specific examples include sodium lauryl sulfate, sodium octylphenol glycolether sulfate, sodium dodecylbenzene sulfonate, sodium lauryl diglycol sulfate, ammonium tritertiarybutylphenol penta- and octa-glycol sulfates, dioctyl sodium sulfosuccinate, alpha-olefin sulfonates and sulfonated biphenyl ethers. Numerous other examples of suitable surfactants are disclosed in U.S. Patent 2,600,831, the disclosure of which in its entirety is incorporated herein by reference.

Those skilled in the art of emulsion polymers will appreciate that protective colloids, fillers, extenders, colorants, tackifiers, and other additives which are compatible with the polymer emulsion can be added, if desired.

The polymerization reaction is typically conducted with agitation at a temperature sufficient to maintain an adequate reaction rate until most or all monomers are consumed. Temperatures of about 120° to about 190° F. (49° to 88° C.) are generally used. Temperatures of about 150° to about 170° F. (66° to 76° C.) are preferred. Monomer addition is usually continued until the latex reaches a polymer concentration of about 20 to about 70 weight percent and preferably about 40 to about 50 weight percent.

A chain transfer agent may be added to the reaction mixture where it is desired to produce a lower molecular weight copolymer. Examples of chain transfer agents, which are added in amounts of about 0.1 to about 5 percent by weight of total monomers, are organic halides such as carbon tetrachloride and tetrabromide, alkyl mercaptans, such as secondary and tertiary butyl mercaptan, and thiol substituted polyhydroxyl alcohols, such as monothiolglycerine.

SOLUTION COPOLYMER

The solution copolymer used with the latex comprises a polymeric composition formed by the solution copolymerization of a mixture containing at least three water soluble comonomers.

The first of these water soluble comonomers has at least one olefinically unsaturated linkage and at least two carboxyl groups, said comonomer having the general formula:

wherein R₁, R₂, and R₃ are independently hydrogen, halogen, nitro, amino, and organic radicals, usually of no more than 10 carbon atoms; R₄ is hydrogen or an organic radical, usually containing no more than about 10 carbon atoms; and X is a covalent bond or an organic radical, usually of no more than about 10 carbon atoms. Normally, the number of all the carbon atoms in comonomer (a) is no greater than 30. Since comonomer (a) contains at least two carboxyl groups, at least one of R₁, R₂, and R₃ must contain a carboxyl group when R₄ is hydrogen or an organic radical containing a carboxyl group, and at least two of R₁, R₂, and R₃ must contain carboxyl groups when R₄ is other than hydrogen or an organic radical containing a carboxyl group.

The term "organic" radical, when used herein, broadly refers to any carbon-containing radical. Such radicals may be cyclic or acyclic, may have straight or branched chains, and can contain one or more hetero atoms such as sulfur, nitrogen, oxygen, phosphorus, and the like. Further, they may be substituted with one or more substituents such as thio, hydroxy, nitro, amino, cyano, carboxyl or halogen. In addition to aliphatic chains, they may contain aryl radicals, including arylalkyl and alkylaryl radicals; and cycloalkyl radicals, including alkyl-substituted cycloalkyl and cycloalkyl-substituted alkyl radicals, with such radicals, if desired, being substituted with any of the substituents listed above. When cyclic radicals are present, whether aromatic or nonaromatic, it is preferred that they have only one ring. Preferred organic radicals are, in general, free of olefinic and alkynyl linkages and also free of aromatic radicals. The term "water soluble" shall denote a solubility in an amount of at least 2.5 percent by weight in deionized water at a temperature of about 90°C . Preferably the comonomers are soluble in water to the extent of at least 5 percent, and most preferably at least 15 percent by weight. In comonomer (a), it is preferred that R₁, R₂, and R₃ be hydrogen or unsubstituted cycloalkyl or unsubstituted, straight or branched chain alkyl radicals which have no more than 7 carbon atoms, with the exception that at least one of R₁, R₂, and R₃ must either be or bear a group,

wherein R₅ is hydrogen or an organic radical, usually having no more than about 10 carbon atoms. In any event, compound (a) must contain at least two carboxyl groups.

More preferably, R₁, R₂, and R₃, except for the group or groups being or bearing the carboxyl or carboxylate group or groups, are hydrogen or unsubstituted, straight or branched chain alkyl radicals having no more than 5 carbon atoms. When X is an organic radical, it preferably has no more than 6 carbon atoms and is an unsubstituted, branched or unbranched chain alkyl or unsubstituted cycloalkyl radical and, when an alkyl radical, is most preferably unbranched.

In the most preferred form of all, comonomer (a) is a dicarboxylic acid wherein R₁, R₂, and R₃ are all independently hydrogen, carboxyl groups, or methyl or ethyl radicals, either unsubstituted or substituted with a carboxyl group, provided that R₁, R₂, and R₃ comprise, in total, one carboxyl group where R₄ is hydrogen or an organic radical containing a carboxyl group and two carboxyl groups where R₄ is other than hydrogen or an organic radical containing a carboxyl group. Most preferred for R₄ and R₅ are hydrogen or unsubstituted alkyl radicals or unsubstituted cycloalkyl radicals. Most preferred for X is a covalentlbond.

particular regard to the most preferred embodiment of the water-soluble comonomer (a), it is preferred that, except for the carboxyl and carboxylate groups, the remainder of the compound be unsubstituted, that is, consist of only carbon and hydrogen atoms, and that the maximum number of carbon atoms in the compound be 27; with R₁ and R₂ combined having no more than 9 carbon atoms, and R₃ no more than 8 carbon atoms; with R₄ and R₅ having no more than 7 carbon atoms. In the very most preferred embodiment, each side of the olefinic linkage has no more than about 5 carbon atoms and both of R₄ and R₅ are hydrogen.

Suitable copolymerizable, water-soluble comonomers (a) according to the above most preferred description include monoolefinically unsaturated diacids, such as methylenesuccinic acid (itaconic acid), the cis- and trans- forms of butenedioic acid (maleic and fumaric acids), both the cis- and trans- forms (where such exist) of the diacids resulting when one or more of the hydrogen atoms on the carbon chains of maleic/fumaric acid or itaconic acid is replaced with a methyl or ethyl radical, and the C₁ to C₅ semi-esters thereof. Of these, itaconic acid is most preferred. The second of these water soluble comonomers has at least one olefini cally unsaturated linkage and a single carboxyl group, said comonomer having the general formula:

wherein R₆, R₇, and R₈ are independently hydrogen, halogen, nitro, amino, and organic radicals, usually of no more than 10 carbon atoms; R₉ is hydrogen or an organic radical, usually containing no more than about 10 carbon atoms; and Y is a covalent bond or an organic radical, usually of no more than about 10 carbon atoms. Normally, the number of all the carbon atoms in comonomer (b) is no greater than 30. Since comonomer (b) contains a single carboxyl group, none of R₆, R₇, and R₈ can contain a carboxyl group where R₉ is hydrogen or an organic radical containing a carboxyl group, and only one of R₆, R₇, and R₈ can contain a carboxyl group where R₉ is other than hydrogen or an organic radical containing a carboxyl group.

In comonomer (b), it is preferred that R₆, R₇, and R₈ be hydrogen or unsubstituted cycloalkyl or unsubstituted, straight or branched chain alkyl radicals which have no more than 7 carbon atoms, with the exception that, where R₉ is other than hydrogen or an organic radical containing a carboxyl group, one of R₆, R₇, and R₈ may either be or bear a carboxyl group. In any event, compound (b) must contain only one carboxyl group. More preferably, R₆, R₇, and R₈, except for the group being or bearing the carboxyl group, are hydrogen or unsubstituted, straight or branched chain alkyl radicals having no more than 5 carbon atoms. When Y is an organic radical, it preferably has no more than 6 carbon atoms and is an unsubstituted, branched or unbranched chain alkyl or unsubstituted cycloalkyl radical and, when an alkyl radical, is most preferably unbranched.

In the most preferred form of all, comonomer (b) is a monocarboxylic acid wherein R₆, R₇, and R₈ are all independently hydrogen or methyl or ethyl radicals, either unsubstituted or substituted with a carboxyl group, provided that R₆, R₇, and Rg comprise, in total, one carboxyl group where R₉ is other than hydrogen or an organic radical containing a carboxyl group. Most preferred for R₉ are hydrogen or unsubstituted alkyl or cycloalkyl radicals. Most preferred for Y is a covalent bond.

In particular regard to the most preferred embodiment of the water-soluble comonomer (b), it is still more preferred that, except for the carboxyl and carboxylate groups, the remainder of the compound be unsubstituted, that is, consist of only carbon and hydrogen atoms, and that the maximum number of carbon atoms in the compound be 27; with R₆ and R₇ combined having no more than 9 carbon atoms, and R₈ no more than 8 carbon atoms; with R₉ having no more than 7 carbon atoms. In the very most preferred embodiment, each side of the olefinic linkage has no more than about 5 carbon atoms and R₉ is hydrogen.

Suitable copolymerizable, water-soluble comonomers (b) according to the above most preferred description include monoolefinically unsaturated monocarboxylic acids, such as acrylic acid and methacrylic acid.

The third of these water soluble comonomers is an olefinically unsaturated carboxylic acid hydroxy ester having the general formula:

wherein R₁₀, R₁₁, and R₁₂ are independently selected from hydrogen, halogen, nitro, amino, and organic radicals, usually of no more than 10 carbon atoms; R₁₃ is an organic radical having at least 2, and usually no more than 10, carbon atoms, with at least one of R₁₀, R₁₁, R₁₂, and R₁₃ being an organic radical having a hydroxyl substituent thereon, said hydroxyl substituent being at least 2 carbon atoms away from the carboxylate group; and, where one or more of R₁₀, R₁₁, and R₁₂ is an organic radical having a hydroxyl substituent, R₁₃ preferably is an unsubstituted hydrocarbyl radical, usually of no more than 10 carbon atoms; and Z is a covalent bond or an organic radical, usually of no more than 10 carbon atoms. For comonomer (c), it is preferred that R₁₀, R₁₁, and R₁₂ be free of hydroxyl, carboxyl and carboxylate substituents and, even more preferably, that they be hydrogen or unsubstituted cycloalkyl radicals or unsubstituted, straight or branched chain alkyl radicals, each of which has no more than 7 carbon atoms. Most preferably, R₁₀, R₁₁, and R₁₂ are hydrogen or unsubstituted, straight or branched chain alkyl radicals having no more than 5 carbon atoms. In the very most preferred form of all, R₁₀, R₁₁, and R₁₂ are all independently hydrogen, methyl or ethyl. R₁₃ is also preferably free of carboxyl and carboxylate groups and is most preferably an alkyl or cycloalkyl radical, with the required hydroxyl group being substituted at least 2 carbon atoms away from the carboxylate group. When Z is an organic radical, it is preferably a branched or unbranched chain, unsubstituted alkyl radical or unsubstituted cycloalkyl radical, each having no more than about 6 carbon atoms and, when an alkyl radical, is preferably unbranched. However, most preferred for Z is a covalent bond.

Preferred comonomers (c) are the hydroxy alkyl and hydroxy cycloalkyl esters of acrylic and methacrylic acids and, while the esterifying moiety must have at least 2 carbon atoms, it preferably has no more than about 6 carbon atoms, and, more preferably, no more than about 4 carbon atoms. Of the hydroxy alkyl and hydroxy cycloalkyl esters of acrylic and methacrylic acids meeting these criteria, 2-hydroxyethyl acrylate is most preferred.

The copolymerization is conducted with a large proportion of comonomer (a) compared to either comonomer (b) or comonomer (c). Typically, the copolymerization utilizes about 40 percent to about 60 percent of comonomer (a) by weight of total monomers, with the balance consisting essentially of a mixture of comonomers (b) and (c).

Where comonomers (a), (b), and (c) are copolymerized to form a solution copolymer, that is, where the balance of the mixture of comonomers other than the olefinically unsaturated polycarboxylic acid comonomer consists essentially of a mixture of both an olefinicallly unsaturated monocarboxylic acid and an olefinically unsaturated carboxylic acid hydroxy ester, the monocarboxylic acid and ester can be used in any desired proportions to make up the balance of comonomers used with comonomer (a). For example, as little as about 1% monocarboxylic acid and about 49% hydroxy ester to about 49% monocarboxylic acid and about 1% hydroxy ester can be used. However, substantially equal proportions of monocarboxylic acid and hydroxy ester have been found to be particularly effective in producing the combination of low viscosity and high strength desired in the binders of this invention. Preferably, the comonomeric mixture comprises between about 20 percent and about 30 percent of each of comonomers (b) and (c) and about 40 percent to about 60 percent of comonomer (a). More preferably, the comonomeric mixture comprises between about 25% and about 27% of each of comonomers (b) and (c) and about 46% to about 50% of comonomer (a).

Although it is preferred to copolymerize a mixture containing comonomers (a), (b), and (c) exclusively, in some instances it may be desirable to utilize one or more additional comonomers in relatively small amounts. Thus, for example, the solution copolymeric composition may optionally contain about 0.1 weight percent to about 20 weight percent of one or more polymerizable, monoole-finically unsaturated nonionic comonomers to serve as extenders, T_g modifiers, and the like, without significantly degrading the basic properties of the copolymer. Suitable additive comonomers for such purposes include the C₁ to C₅ saturated esters of acrylic and methacrylic acid, vinylidene chloride and vinyl compounds such as vinyl chloride, vinyl acetate, styrene, and the like. Preferred additive monomers are ethyl acrylate, butyl acrylate and styrene.

Suitable copolymers of comonomers (a), (b), and (c) can be prepared by either thermal or, preferably, free-radical initiated solution polymerization methods. Further, the reaction may be conducted by batch, semi batch, or continuous procedures, which are well known for use in conventional polymerization reactions. Where free-radical polymerization is used, illustrative procedures suitable for producing aqueous copolymer solutions typically involve gradually adding simultaneously the comono mers to be copolymerized to an aqueous reaction medium at rates proportional to the respective percentage of each comonomer in the finished copolymer and initiating and continuing said copolymerization with a suitable polymerization catalyst. Optionally, one or more of the comonomers can be added disproportionately throughout the polymerization so that the copolymer formed during the initial stages of copolymerization will have a composition differing from that formed during the intermediate and later stages of the same copolymerization.

Illustrative water-soluble, free-radical initiators are hydrogen peroxide and an alkali metal (sodium, potassium, or lithium) or ammonium persulfate, or a mixture of such an initiator in combination with a reducing agent activator, such as a sulfite, more specifically an alkali metabisulfite, hyposulfite or hydrosulfite; or glucose, ascorbic acid, erythorbic acid or other reducing agent, to form a "redox" system. Normally the amount of initiator used ranges from about 0.01 percent to about 5 percent, by weight, based on the comonomer charge. In a redox system, a corresponding range (about 0.01 to about 5 percent) of reducing agent is normally used.

The copolymerization, once started, is continued, with agitation, at a temperature sufficient to maintain an adequate reaction rate until most, or all, of the comonomers are consumed and until the solution reaches a polymer solids concentration between about 5 percent and about 40 percent, by weight. Reaction temperatures in the range of about 10°C to about 100ºC will yield satisfactory polymeric compositions. When persulfate systems are used, the solution temperature is normally in the range of about 60°C to about 100°C, while in redox systems, the temperature is normally in the range of about 10°C to about 70°C, and preferably about 30ºC to about 60°C. At this point, the solution normally will have a viscosity in the range between about 10 cps and about 1000 cps at a solids content of 15 percent at pH 3.

In general, the solution copolymer is used with the emulsion polymer latex in an amount of about 1 percent to about 20 percent dry weight. Preferably, the solution copolymer is present in a concentration of about 2 percent to about 5 percent. The desired amount of solution copolymer is added to the emulsion polymer latex and the pH of the resulting blend is adjusted to about pH 5 to about pH 9 prior to using as a binder.

Textile substrates useful in the articles of this invention include assemblies of fibers, preferably fibers which contain polar functional groups. Significantly greater improvements in tensile strength and other physical properties are achieved by application of the binders of the present invention to natural or synthetic polar group-containing fibers in contrast to relatively nonpolar fibers such as untreated, nonpolar polyolefin fibers. However, such nonpolar fibers also can be employed. Furthermore, polar groups, such as carbonyl (e.g., keto) and hydroxy groups, can be intro duced into polyolefins, styrene-butadiene polymers and other relatively nonpolar fibers by known oxidation tech niques, and it is intended that such treated polymers can be employed in the articles and methods of this invention.

For the purposes of this invention, it is intended that the term "fibers" encompass relatively short filaments or fibers as well as longer fibers often referred to as "filaments." Illustrative polar functional groups contained in suitable fibers are hydroxy, etheral, carbonyl, carboxylic acid (including carboxylic acid salts), carboxylic acid esters (including thio esters), amides, amines etc. Essentially all natural fibers include one or more polar functional groups. Illustrative are virgin and reclaimed cellulosic fibers such as cotton, wood fiber, coconut fiber, jute, hemp, etc., and protenaceous materials such as wool and other animal fur. Illustrative synthetic fibers containing polar functional groups are polyesters, polyamides, carboxylated styrenebutadiene polymers, etc. Illustrative polyamides include nylon-6, nylon-66, nylon-610, etc.; illustrative polyesters include "Dacron," "Fortrel," and "Kodel"; illustrative acrylic fibers include "Acrilan," "Orion," and "Creslan." Illustrative modacrylic fibers include "Verel" and "Dynel." Illustrative of other useful fibers which are also polar are synthetic carbon, silicon, and magnesium silicate (e.g., asbestos) polymer fibers and metallic fibers such as aluminum, gold, and iron fibers.

These and other fibers containing polar functional groups are widely employed for the manufacture of a vast variety of textile materials including wovens, nonwovens, knits, threads, yarns, and ropes. The physical properties of such articles, in particular tensile strength, abrasion resistance, scrub resistance, and/or shape retention, can be increased by addition of the binders of the present invention with little or no degradation of other desirable properties such as hand, flexibility, elongation, and physical and color stability.

The binders of the present invention can be applied to the selected textile material by any one of the procedures employed to apply other polymeric materials to such textiles. Thus, the textile can be immersed in the binder dispersion in a typical dip-tank operation, sprayed with the binder dispersion, or contacted with rollers or textile "printing" apparatus employed to apply polymeric dispersions and solutions to textile substrates.

The concentration of binder in the applied dispersion can vary considerably depending primarily upon the application apparatus and procedures employed and desired total polymer loading (polymer content of finished textile). Thus, binder concentration can vary from as low as about 1 percent to as high as 60 percent or more, although most applications involve the use of dispersions containing about 5 to about 60 weight percent solids.

Textile fiber assemblies wetted with substantial quantities of binder are typically squeezed with pad roll, nip roll, and/or doctor blade assemblies to remove excess dispersion and, in some instances, to "break" and coalesce the polymer or polymers constituting the binder and improve polymer dispersion and distribution and binder- fiber wetting. The binder- containing fiber assembly can then be allowed to cure at ambient temperature by evaporation of solvent or water, although curing is typically accelerated by exposure of the binder-containing fiber assembly to somewhat elevated temperatures such as 90° C. to 200° C. One particular advantage of the binders of the present invention is that they cure relatively fast. Thus, bond strength between the binder and fibers, and thus, between respective fibers, develops quickly.

Rapid cure rate is important in essentially all methods of applying polymers to textiles since it is generally desirable to rapidly reduce surface tackiness and increase fiber-to-fiber bond strength. This is particularly true in the manufacture of loose woven textiles, knits, and nonwovens, including all varieties of paper. Most often, adequate bond strength and sufficiently low surface tackiness must be achieved in such textiles before they can be subjected to any significant stresses and/or subsequent processing. While cure rate can be increased with more severe curing conditions, i.e., using higher temperatures, such procedures require additional equipment, increased operating costs, and are often unacceptable due to adverse effects of elevated temperatures on the finished textile.

The binder content of the finished textile can vary greatly depending on the extent of improvement in physical properties desired. For instance, very minor amounts of binder are sufficient to increase tensile strength, shape retention, abrasion resistance (wear resistance), and/or wet-scrub resistance of the textile fiber assembly. Thus, binder concentrations of at least about 0.1 weight percent, generally at least about 0.2 weight percent, are sufficient to obtain detectable physical property improvements in many textiles. However, most applications involve binder concentrations of at least about 1 weight percent and preferably at least about 2 weight percent based on the dry weight of the finished binder-containing textile article. Binder concentrations of about 1 to about 95 weight percent can be employed, while concentrations of about 1 to about 30 weight percent based on finished textile dry weight are most common.

The product property in which the most significant improvement results depends, at least to some extent, on the structure of the treated fiber assemblage. For instance, threads and ropes formed from relatively long, tightly wound or interlaced fibers and tightly woven textiles generally possess significant tensile strength in their native state, and the percentage increase in tensile strength resulting from incorporation of binder will be less, on a relative basis, than it is with other products such as loose-wovens, knits, and non-wovens. More specifically, significant improvements in abrasion resistance and scrub resistance are achieved in threads, ropes, and tightly woven textiles, and significant improvement in tensile strength (both wet and dry) can be realized in such products which are manufactured from relatively short fibers and which thus have a relatively lower tensile strength in their native form. Usually the most significant improvements sought in loose-woven textiles are shape retention (including retention of the relative spacing of adjacent woven strands), abrasion resistance, and scrub resistance, and these improvements can be achieved by the methods and with the articles of this invention. Similar improvements are also obtained in knitted fabrics.

The most significant advantages of the useful methods and textile articles are in the field of nonwovens. Non-wovens depend primarily on the strength and persistence of the fiber-binder bond for their physical properties and for the retention of such properties with use. Bonded non-woven fabrics, such as the textile articles of this invention, can be defined generally as assem blies of fibers held together in a random or oriented web or mat by a bonding agent. While many non-woven materials are manufactured from crimped fibers having lengths of about 0.5 to about 5 inches, shorter or longer fibers can be employed. The utilities for such non-wovens range from hospital sheets, gowns, masks, and bandages to roadbed underlayment supports, diapers, roofing materials, napkins, coated fabrics, papers of all varieties, tile backings (for ungrouted tile prior to installation), and various other utilities too numerous for detailed listing. Their physical properties range all the way from stiff, board-like homogeneous and composite paper products to soft drapeable textiles (e.g., drapes and clothing), and wipes. The myriad variety of non-woven products can be generally divided into categories characterized as "flat goods" and "highloft" goods, and each category includes both disposable and durable products. Presently, the major end uses of disposable flat goods non-wovens include diaper cover stock, surgical drapes, gowns, face masks, bandages, industrial work clothes, and consumer and industrial wipes and towels such as paper towels, and feminine hygiene products. Current major uses of durable flat goods non-wovens include apparel interlinings and interfacings, drapery and carpet backings, automotive components (such as components of composite landau automobile tops), carpet and rug backings, and construction materi als, such as roadbed underlayments employed to retain packed aggregate, and components of composite roofing materials, insulation, pliable or flexible siding and interior wall and ceiling finishes, etc.

The so-called "highloft" non-wovens can be defined broadly as bonded, non-woven fibrous structures of varying bulks that provide varying degrees of resiliency, physical integrity, and durability depending on end use. Currently, major uses of highloft non-wovens include the manufacture of quilts, mattress pads, mattress covers, sleeping bags, furniture underlayments (padding), air filters, carpet underlayments (e.g., carpet pads), winter clothing, shoulder and bra pads, automotive, home, and industrial insulation and paddings, padding and packaging for stored and shipped materials and otherwise hard surfaces (e.g., automobile roof tops, chairs, etc.), floor care pads for cleaning, polishing, buffing, and stripping, house robes (terrycloth, etc.), crib kick pads, furniture and toss pillows, molded packages, and kitchen and industrial scrub pads.

The binders and methods can be used to manufacture all such non-wovens, and they are particularly useful for the manufacture of non-wovens free of, or having reduced levels of formaldehyde or other potentially toxic components and which have relatively high wet and dry tensile strength, abrasion resistance, color stability, stability to heat, light, detergent, and solvents, flexi bility, elongation, shape retention, and/or acceptable "hand." They are also particularly useful in manufacturing methods which require relatively short cure time (rapid bonding rate), relatively high binder-to-fiber adhesion, temperature stability (during curing and subsequent treatment), and/or the use of slightly acidic, neutral or alkaline application solutions or dispersions.

The binder compositions can also be employed to bind two or more substrates to each other or to coat such substrates and, thus, can be employed as coatings and adhesives for forming laminates or other composite articles and for assembling adhesive-bound structures. Illustrative of such uses are binding or formation of laminates of substrates such as acrylates, terephthalates, cellulosics (e.g., wood, paper, etc.), phenolic resins, urethane, metals, and the like; adhering carpet backing to tufted or woven carpets, bonding vapor barriers (plastic films) to insulation, wall board, etc., adhering tiles or other wall or floor coverings to concrete, wallboard, wood or other structural materials, application of wood veneers to wood or composite backings, and numerous other similar adhesive applications.

When the binder compositions are used as coatings for any one of a variety of substrates, such as those identified immediately above, they may also contain one or more other ingredients, if desired, so long as such ingre dients do not prevent hardening, or the compositions can be employed simply as clear coatings . Illustrative , optional ingredients include colorants , such as dyes and pigments, heat and ultra-violet stabilizers, accelerators for hardening the copolymers constituting the binders of the present invention , plasticizers , etc . Films and coatings may then be deposited , for example , by Weir coating, i. e. application of the binder from a bath thereof having a controlled overflow, or by brush, spray or doctor- or air-knife coating, by dip coating, etc . , and the products may then be cured at ambient or elevated temperatures . Binder concentrations suitable for use in coatings and adhesives are similar to those described hereinabove for textile binders . However, most binding applications , other than textile binding , and coating applications , such as clear coatings and paints , will generally involve binder concentrations of at least about 5 weight percent , typically at least about 10 weight percent of the total composition. The invention will be further described in the following examples which are illustrative of specific modes of practicing the invention and are not intended to limit the scope of the invention as defined in the claims . All percentages are by weight unless otherwise specified . All "parts" of solutions refer to dry weights of the specified active component, rather than "wet" weights . EXAMPLE 1

A styrene-butadiene-itaconic acid copolymer latex was prepared by adding to a pressure reactor with constant stirring 34.7 parts water, 1 part itaconic acid, 0.8 part of a 10% solution of Aerosol A-196 surfactant (sodium dicyclohexyl sulfosuccinate available from American Cyanamid Co., Wayne, New Jersey), and 1 part of a polystyrene seed, 25 nm particle size. The mixture was heated to 165°F (74° C.) and 0.2 part sodium persulfate was added to initiate the reaction. Then 40 parts butadiene, 60 parts styrene, 1.0 part Sulfole 120 mercaptan (tertiary dodecyl mercaptan available from Phillips Chemical Co., a subsidiary of Phillips Petroleum Co., Bartles- ville, Oklahoma) dissolved in styrene, an additional 0.5 part sodium persulfate, an additional 1.5 parts Aerosol A-196, 0.03 part Versene 100 (sodium ethylene diamine tetraacetate available from Dow Chemical Co., Midland, Michigan), 4 parts itaconic acid, and 58.5 parts water were added over a 6 hour period. The final mixture was heated at a temperature of 190°F (88° C.) for 5 hours. The resulting emulsion polymer was cooled and removed from the reactor. It had a pH value of 2.2, which was adjusted to pH 7.0 with ammonium hydroxide. Total solids were 44.1 percent. Viscosity was measured with a Brookfield Model RVF viscometer at 20 rpm and found to be 360 cps. Average particle size was 122 nm. EXAMPLE 2

A solution copolymer was prepared by heating a mixture of 147 grams itaconic acid, 74 grams acrylic acid, 74 grams 2-hydroxyethyl acrylate, and 1147 grams deionized water to a temperature of 80°C and adding 2.9 grams sodium persulfate dissolved in 26.5 grams deionized water. The resulting mixture was then maintained at 80°C. An additional 2.9 gram quantity of sodium persulfate dissolved in 26.5 grams deionized water was added after 3 hours. After 6 hours the pH value of the resultant solution copolymer was adjusted to pH 4.0 with concentrated sodium hydroxide. The solution copolymer was then cooled and filtered. Viscosity was 24 cps at 17% total solids.

EXAMPLE 3

The procedure of Example 2 was followed except that ammonium persulfate was used as the initiator instead of sodium persulfate and the pH of the solution copolymer was adjusted to pH 4.0 using ammonium hydroxide instead of sodium hydroxide. Viscosity was 29 at 18% total solids.

The following example illustrates the preparation of a binder according to the present invention.

EXAMPLE 4

The solution copolymer of Example 2 was mixed with the emulsion polymer latex of Example 1 in a concentration of 4% by weight based on the emulsion copolymer latex and the pH was adjusted to pH 6 with sodium hydroxide and then to pH 9 with ammonium hydroxide. Viscosity was 15 cps at 25% total solids, 27 cps at 30% total solids, and 275 cps at 35% total solids. Wet tensile strength was measured by padding Whatman No. 4 paper and curing between metal plates at 188°C for periods of 4 seconds, 6 seconds, and 8 seconds, and at 150°C for 180 seconds. The wet tensile strength is reported as the percentage of the wet tensile strength obtained under the same conditions with a widely used reference commercial cellulose binder composition comprising a carboxylated SBR latex (53.4 % butadiene, 43.7 % styrene, 1.9 % N-methylol acrylamide, and 0.5% each of acrylamide and itaconic acid) cross-linked with 6% methoxymethyl melamine (Cymel 303). The wet tensile strength after curing was found to be 59% at 4 seconds, 79% at 6 seconds, 89% at 8 seconds, and 118% at 180 seconds.

The results obtained in the foregoing example show that a binder visosity of less than about 20 cps at 25% total solids, less than about 30 cps at 30% total solids, and less than about 280 cps at 35% total solids can be realized using a solution copolymer obtained by polymerizing equal parts of itaconic acid and a mixture of equal parts of acrylic acid and 2-hydroxyethyl acrylate in accordance with the present invention. The results also show that wet tensile strengths of about 60% to about 120% of those obtained using a standard formaldehyde emitting reference binder can be realized.

The following example illustrates the preparation of a binder utilizing another solution copolymer of the present invention.

EXAMPLE 5

The solution copolymer of Example 3 was mixed with the emulsion polymer latex of Example 1 in a concentration of 4% by weight based on the emulsion copolymer latex and the pH was adjusted to pH 6 with sodium hydroxide and then to pH 9 with ammonium hydroxide. Viscosity was 15 cps at 25% total solids, 58 cps at 30% total solids, and 616 cps at 35% total solids. Wet tensile strength after curing was found to be 54% at 4 seconds, 71% at 6 seconds, 83% at 8 seconds, and 111% at 180 seconds.

The results obtained in the foregoing example show that a binder viscosity of less than about 20 cps at 25% total solids, less than about 60 cps at 30% total solids, and less than about 620 cps at 35% total solids can be realized using a solution copolymer obtained by copolymerizing equal parts of itaconic acid and a mixture of equal parts of acrylic acid and 2-hydroxyethyl acrylate in accordance with the present invention. The results also show that wet tensile strengths of about 55% to about 110% pf those obtained using a standard formaldehyde emitting reference binder can be realized. The binders of the present invention are characterized by low viscosities. In general, viscosities in the range of about 2 cps at 25% total solids to about 1000 cps at 35% total solids depending upon the solution copolymer content of the binder can be realized by using aqueous solution copolymers produced by copolymerizing mixtures of olefinically unsaturated polycarboxylic acids, olefinically unsaturated monocarboxylic acids, and olefinically unsaturated carboxylic acid hydroxy esters in accordance with the present invention. Especially preferred are viscosities of under about 20 cps, which are realizable at 25% total solids where 4% solution copolymer is used. Where lower concentrations of solution copolymer are used, viscosities of under about 20 cps may be realized at higher total solids content. The binders of the present invention do not emit formaldehyde and are fast curing. While they have unexpectedly low viscosities, the binders of the present invention display satisfactory tensile strengths compared to binders obtained by using formaldehyde-emitting cross-linking agents. This invention may be embodied in other forms without departing from the spirit or essential character istics thereof. For example, it is recognized that while the description of the present invention and the pre ferred embodiments thereof are all directed toward binders incorporating a solution copolymer which is the product of copolymeriza tion of an olefinically unsaturated polycarboxylic acid, an olefinically unsaturated monocarboxylic acid, and an olefinically unsaturated carboxylic acid hydroxy ester, there are applications wherein the inclusion of an additional comonomer capable of imparting specific properties to the resulting copolymer and in turn to the binder formulated with such copolymer may be desirable. Consequently, the present embodiments and examples are to be considered only as being illustrative and not restrictive, with the scope of the invention being indicated by the appended claims. All embodiments which come within the scope and equivalency of the claims are, therefore, intended to be embraced therein.

Claims

I claim:

1. A fast-curing binder for textile substrates comprising an admixture of an aqueous emulsion copolymer latex and the product of copolymerization, in aqueous solution, of a mixture comprising:

one or more first water-soluble comonomers having the general formula:

wherein R₁, R₂, and R₃ are independently selected from the group consisting of hydrogen, halogen, nitro, amino, and organic radicals; R₄ is hydrogen or an organic radical; and X is a covalent bond or an organic radical; each of said one or more first water-soluble comonomers containing at least two carboxyl groups;

one or more second water-soluble comonomers having the general formula:

wherein R₆, R₇, and R₈ are independently selected from the group consisting of hydrogen, halogen, nitro, amino, and organic radicals; R₈ and R₉ are hydrogen or organic radicals; and Y is a covalent bond or an organic radical; each of said one or more second water-soluble comonomers containing a single carboxyl group; and

one or more third water soluble comonomers having the general formula:

wherein R₁₀, R₁₁, and R₁₂ are independently selected from the group consisting of hydrogen, halogen, nitro, amino, and organic radicals; R₁₃ is an organic radical having at least 2 carbon atoms and at least one hydroxyl substituent thereon; and Z is an organic radical or a covalent bond; said one or more first water-soluble comonomers being present in said mixture in a concentration of about 40% to about 60% by weight of total monomers;

said product of copolymerization being present in said admixture in a concentration of about 1% to about 20%, by dry weight of said latex.

2. A binder according to claim 1 wherein said latex is selected from the group consisting of non-formaldehyde emitting styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/acrylate, and all-acrylate copolymer latexes.

3. A binder according to claim 1 wherein said product of copolymerization is admixed with said non-formaldehyde emitting aqueous emulsion copolymer latex in an amount of about 2% to about 5%, by dry weight of said latex.

4. A fast-curing, zero formaldehyde binder for textile substrates comprising an admixture of a non-formaldehyde emitting aqueous emulsion copolymer latex selected from the group consisting of styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/acrylate and all-acrylate copolymer latexes, and the product of copolymerization, in aqueous solution, of a mixture comprising: one or more first water soluble comonomers selected from the group consisting of the cis and trans forms of butenedioic acid and methylenesuccinic acid, the diacids resulting when one or more of the hydrogen atoms on the carbon chains of butenedioic acid or methylenesuccinic acid is replaced with methyl or ethyl groups, and the C ₁ to C₅ semi-esters of said acids;

one or more second water soluble comonomers selected from the group consisting of acrylic acid and methacrylic acid; and

one or more third water soluble comonomers selected from the group consisting of the C₂ to C₄ hydroxyalkyl esters of acrylic acid and methacrylic acid;

said product of copolymerization being admixed with said latex in an amount of about 1% to about 20%, by weight, based on said latex, said first water-soluble comonomer being present in said mixture in a concentration of about 40% to about 60% by weight of total monomers.

5. A fast-curing, zero formaldehyde binder for textile substrates comprising an admixture of the product of copolymerization, in aqueous solution, of a mixture of comonomers comprising itaconic acid, acrylic acid, and 2- hydroxyethyl acrylate, said mixture comprising about 40% to about 60%, by weight of total monomers, of itaconic acid, with a non-formaldehyde emitting aqueous emulsion copolymer latex selected from the group consisting of styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/acrylate and all-acrylate copolymer latexes, in a concentration of about 2% to about 5%, by dry weight, based on said latex.

6. A fast-curing, zero formaldehyde binder for textile substrates comprising an admixture of the product of copolymerization, in aqueous solution, of a mixture of comonomers comprising itaconic acid, methacrylic acid, and 2-hydroxyethyl acrylate, said mixture comprising about 40% to about 60%, by weight of total monomers, of itaconic acid, about 20% to about 30% of acrylic acid, and about 20% to about 30% of 2-hydroxyethyl acrylate, with a non-formaldehyde emitting aqueous emulsion copolymer latex selected from the group consisting of styrene-butadiene, vinyl acetate/acrylate and all-acrylate copolymer latexes, in an amount of about 2% to about 5%, by dry weight, based on said latex.

7. A fast-curing, zero formaldehyde binder for textile substrates comprising an admixture of the product of copolymerization, in aqueous solution, of a mixture of comonomers comprising about 40% to about 60%, by weight of total monomers, of itaconic acid, the balance of said mixture comprising a mixture of about 1% to about 49% acrylic acid and about 1% to about 49% 2-hydroxyethyl acrylate, with a non-formaldehyde emitting aqueous emulsion copolymer latex selected from styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/acrylate and all-acrylate copolymer latexes, in an amount between about 2% and about 5%, by dry weight, based on said latex.

8. A binder according to claim 1 wherein said latex is a carboxylated styrene-butadiene copolymer latex containing about 0.5% to about 5% of itaconic acid, by weight of total monomers.

9. A binder according to claim 1 wherein said mixture additionally contains about 0.1% to about 20% by weight of one or more polymerizable, monoolefinically unsaturated nonionic comonomers.

10. A binder according to claim 9 wherein said one or more polymerizable, monoolefinically unsaturated nonionic comonomers is selected from the group consisting of the C₁ to C₅ saturated esters of acrylic acid and methacrylic acid, vinylidene chloride, vinyl chloride, vinyl acetate, and styrene.

11. A binder according to claim 1 having a viscosity of less than about 20 cps at 25% total solids.

12. A binder according to claim 1 wherein the viscosity of said binder is in the range of about 2 cps at 25% total solids to about 1000 cps at 35% total solids.

13. A process for preparing a fast-curing binder for textile substrates comprising:

copolymerizing, in aqueous solution, a mixture comprising:

one or more first water-soluble comonomers having the general formula:

one or more second water-soluble comonomers

having the general formula:

wherein R₆, R₇, and R₈ are independently selected from the group consisting of hydrogen, halogen, nitro, amino, and organic radicals; R₉ is hydrogen or an organic radical; and Y is a covalent bond or an organic radical, each of said one or more second water-soluble comonomers containing a single carboxyl group; and

one or more third water soluble comonomers having the general formula:

wherein R₁₀, R₁₁, and R₁₂ are independently selected from the group consisting of hydrogen, halogen, nitro, amino, and organic radicals; R₁₃ is an organic radical having at least 2 carbon atoms and at least one hydroxyl substituent thereon; and Z is an organic radical or a covalent bond;

said one or more first water-soluble comonomers being present in said mixture in a concentration of about 40% to about 60% by weight of total monomers; to produce an aqueous solution copolymer; and

admixing said solution copolymer with an aqueous emulsion copolymer latex in a concentration of about 1% to about 20%, by dry weight of said latex.

14. A process for preparing a fast-curing, zero formaldehyde binder for textile substrates comprising:

copolymerizing, in aqueous solution, a mixture comprising:

one or more first water soluble comonomers selected from the group consisting of the cis and trans forms of butenedioic acid and methylenesuccinic acid, the diacids resulting when one or more of the hydrogen atoms on the carbon chains of butenedioic acid or methylenesuccinic acid is replaced with methyl or ethyl groups, and the C₁ to C₅ semi-esters of said acids;

said first water-soluble comonomer being present in said mixture in a concentration of about 40% to about 60% by weight of total monomers;

to produce an aqueous solution copolymer; and admixing said soution copolymer with a non-formaldehyde emitting aqueous emulsion copolymer latex selected from the group consisting of styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/acrylate and all-acrylate copolymer latexes, in a concentration of about 1% to about 20%, by dry weight of said latex.

15. A process for preparing a fast-curing, zero formaldehyde binder for textile substrates compris ing:

copolymerizing, in aqueous solution, a mixture of comonomers comprising about 40% to about 60%, by weight of total monomers, of itaconic acid, the balance of said mixture comprising a mixture of acrylic acid and 2-hydroxyethyl acrylate to produce an aqueous solution copolymer; and

admixing said solution copolymer with a non-formaldehyde emitting aqueous emulsion copolymer latex selected from the group consisting of styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/acrylate and all-acrylate copolymer latexes in a concentration of about 1% to about 20%, by dry weight of said latex.

16. A process according to claim 13 wherein said binder has a viscosity of less than about 20 cps at 25% total solids.

17. A process according to claim 13 wherein the viscosity of said binder is in the range of about 2 cps at 25% total solids to about 1000 cps at 35% total solids.

18. An article of manufacture comprising a textile substrate having applied thereto a binder comprising an admixture of an aqueous emulsion copolymer latex and the product of copolymerization, in aqueous solution, of a mixture comprising:

one or more first water-soluble comonomers having the general formula:

one or more second water-soluble comonomers having the general formula:

one or more third water-soluble comonomers having the general formula:

said one or more first water-soluble comonomers being present in said mixture in a concentration of about 40% to about 60% by weight of total monomers;

19. An article according to claim 18 wherein said latex is selected from the group consisting of non-formaldehyde emitting styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/acrylate, and all-acrylate copolymer latexes.

20. An article according to claim 18 wherein said product of copolymerization is admixed with said non-formaldehyde emitting aqueous emulsion copolymer latex in an amount of about 2% to about 5%, by dry weight of said latex.

21. An article of manufacture comprising a textile substrate having applied thereto a fast-curing, zero formaldehyde binder comprising an admixture of a non-formaldehyde emitting aqueous emulsion copolymer latex selected from the group consisting of styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/acrylate and all-acrylate copolymer latexes, and the product of copolymerization, in aqueous solution, of a mixture comprising: one or more first water soluble comonomers selected from the group consisting of the cis and trans forms of butenedioic acid and methylenesuccinic acid, the diacids resulting when one or more of the hydrogen atoms on the carbon chains of butenedioic acid or methylenesuccinic acid is replaced with methyl or ethyl groups, and the C₁ to C₅ semi-esters of said acids;

said product of copolymerization being admixed with said latex in a concentration of about 2% to about 5%, by dry weight of said latex, said first water-soluble comonomer being present in said mixture in a concentration of about 40% to about 60% by weight of total monomers.

22. An article of manufacture comprising a textile substrate having applied thereto a fast-curing, zero formaldehyde binder comprising an admixture of the product of copolymerization, in aqueous solution, of a mixture of comonomers comprising itaconic acid, acrylic acid, and 2-hydroxyethyl acrylate, said mixture comprising about 40% to about 60%, by weight of total monomers, of itaconic acid, said product of copolymerization being admixed with a non-formaldehyde emitting aqueous emulsion copolymer latex selected from the group consisting of styrene-butadiene, carboxylated styrene-butadiene, vinyl acetate/acrylate and all-acrylate copolymer latexes, in a concentration of about 2% to about 5%, by dry weight of said latex.

23. An article according to claim 18 wherein said latex is a carboxylated styrene-butadiene copolymer latex containing about 0.5% to about 5% of itaconic acid, by weight of total monomers.

24. An article according to claim 18 wherein said mixture additionally contains about 0.1% to about 20% by weight of one or more polymerizable, monoolefinically unsaturated nonionic comonomers.

25. An article according to claim 24 wherein said one or more polymerizable, monoolefinically unsaturated nonionic comonomers is selected from the group consisting of the C ₁ to C₅ saturated esters of acrylic acid and methacrylic acid, vinylidene chloride, vinyl chloride, vinyl acetate, and styrene.

26. An article according to claim 18 wherein the viscosity of said binder is less than about 20 cps at 25% total solids.

27. An article according to claim 18 wherein the viscosity of said binder is in the range of about 2 cps at 25% total solids to about 1000 cps at 35% total solids.

28. A process for preparing a high strength textile material which comprises applying to a textile substrate a fast-curing, zero formaldehyde binder comprising an admixture of a non-formaldehyde emitting aqueous emulsion copolymer latex and the product of copolymerization, in aqueous solution, of a mixture comprising:

one or more first water-soluble comonomers having the general formula:

one or more second water-soluble comonomers having the general formula:

one or more third water-soluble comonomers having the general formula:

said one or more first water-soluble comonomers being present in said mixture in a concentration of about 40% to about 60% by weight of total monomers; and

curing the resulting binder-coated substrate.

29. A process according to claim 28 wherein the viscosity of said binder is less than about 20 cps at 25% total solids.

30. A process according to claim 28 wherein the viscosity of said binder is in the range of about

2 cps at 25% total solids to about 1000 cps at 35% total solids.