WO2000000691A1

WO2000000691A1 - Stain resistant polymers and compositions

Info

Publication number: WO2000000691A1
Application number: PCT/US1999/014540
Authority: WO
Inventors: Paule Leigh Allee; Michael S. Williams
Original assignee: Peach State Labs, Inc.
Priority date: 1998-06-30
Filing date: 1999-06-28
Publication date: 2000-01-06
Also published as: AU4836999A

Abstract

The present invention relates to polymers of resol polymers and itaconic acid suitable as stains resist polymer compositions for treatment of fibers and fabrics, in particular nylon. The stain resist compositions of the present invention are resistant to photooxidative yellowing, and can be applied in the dyebath. In addition, the stain resists are not affected by application of fluoropolymer soil resist agents.

Description

STAIN RESISTANT POLYMERS AND COMPOSITIONS

This application claims benefit under 35 U.S.C. § 119(e) of the filing dates of U.S. Provisional Applications Serial Nos. 60/124,053, filed March 12, 1999, and 60/091,208, filed June 30, 1998, the entire contents of each of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention The present invention relates to stain resistant compositions suitable for treating fibers for fabrics and carpet. More particularly, the present invention relates to polymer compositions that can be applied to the fibers, which can include any polyamide fibers, such as nylon (Type 6 and Type 6,6, wool, or silk) to provide superior stain resistance thereto. 2. Description of the Related Art

Many fibers and fabrics, in particular certain articles of apparel and the face cloth or wear surfaces of carpeting, are made of synthetic fibers, including nylons or a nylon blend. Nylon has many desirable properties in such uses. It is inexpensive, easy to manufacture and dye, and has desirable mechanical properties that give it good resilience and "bounce back" after furniture has been moved from the carpet or in traffic areas.

However, a significant drawback to the use of nylon is that it is stainable by anionic stains and dyes, including many substances commonly occurring in items found in households, offices, and industrial settings. Coffee, mustard, wine, and soft drinks are among the many possible stain materials that can ruin nylon and polyester carpeting and fabrics. In order to address this drawback, attempts have been made to provide the fabrics, such as nylon and polyester, with stain resistance through various means, typically involving chemically treating the nylon to provide some form of stain resistance. Fluorochemical treatments have been used in order to provide soil resistance to fabrics and fibers. These are marginally effective in providing some stain resistance, since they prevent wetting of the surface of the fibers or fabric. This minimizes chemical contact between the carpet surfaces and stain causing materials in the short term, and can make some soiling easier to remove. However, fluoropolymer soil resists do not provide adequate protection against anionic dyes and stains found in many of the materials mentioned above. Another approach to this problem has been to treat the fibers with anionic stain resist polymers. These polymers are often sulfonated formaldehyde phenol or naphthol condensation polymers, typically novolac polymers that are cured to form resins. Formaldehyde phenol/naphthol condensation polymers can generally be categorized in two ways. Novolac polymers or resins are "two-stage" resins and are produced with only part of the formaldehyde necessary to stoichiometrically react with the phenol or naphthol. Novolacs are produced by reaction of the formaldehyde and phenolic compound in the presence of an acid catalyst. The acid catalyst reacts with formaldehyde to form a protonated formaldehyde molecule, which in turn substitutes onto the phenolic compound at a position para to the hydroxy moiety. The hydrated carbonium ion and alcohol group on the substituted phenolic compound decomposes, forming a reactive intermediate that can react with another molecule of phenolic compound to produce a diphenolic compound where the two rings are linked by a methylene group. Novolacs are thermosetting resins whose curing reaction is carried out in the presence of hexamethylenetetramine. On heating, the hexamethylenetetramine catalyzes crosslinking of the diphenolic compound into an infusible solid resin.

Resol polymers or resins are also condensation polymers of phenolic compounds and formaldehyde, but have very different structures, properties, and chemistries from those of the novolac polymers or resins. Condensation of resol polymers is initiated by a basic catalyst (not acidic like novolacs) and occurs in the presence of abundant formaldehyde. The intermediate formed is not a para-substituted hydroxylated carbonium compound, as with novolacs. Instead, the alkaline catalyst abstracts a hydrogen from the phenol, forming a phenol anion that reacts with the formaldehyde to yield a methylolphenol anion. This anion continues to react with formaldehyde until the ortho and para sites are fully substituted (in the case of phenol, with methylol groups ~ other phenolic compounds may have one or more ortho or para sites occupied by other functional groups). These substituted phenolic compounds then condense, with the methylol groups combining to form a polymer chain, which can then be crosslinked (without the need for hexamethylenetetramine or other curing catalyst) into a solid resin. The novolac polymers and resins used as stain resists are believed to provide stain resistance by one or more different mechanisms. Ionic bonding of anionic moieties (such as sulfonate and deprotonated hydroxyl moieties) in the stain resist polymer to cationic moieties on the fiber polymer (such as protonated amide moieties in nylon) can both protect the cationic moieties from reaction with the stain material and electrostatically repel the anionic stain material from the vicinity of the reactive cationic site. In addition, bonding to stain materials typically occurs in the amorphous regions of the polymer, rather than in the crystalline regions. The electrostatic and steric blocking of these amorphous regions by the stain resist polymer can prevent the stain materials from diffusing into the fiber. Finally, the stain resist polymer can form a film on the surface of the fiber, which can have a positive effect on the soiling characteristics of the fiber, for example by flaking off of the film with the attached soil.

Other approaches have used acrylic acid polymers, such as polymers of substituted acrylic acids with sulfonated aromatic formaldehyde condensation products, polyacrylic acids or aromatic condensation polymers of an acrylic acid with a hydroxyaromatic ester as the stain resistant polymer coating.

Examples of stain resist compositions and treatments are disclosed in U.S. Patent No. 4,501,591, U.S. Patent No. 4,592,940, U.S. Patent No. 4,680,212, U.S. Patent No. 4,822,373, U.S. Patent No. 4,937,123, U.S. Patent No. 4,940,757, U.S. Patent No. 5,061,763, and U.S. Patent No. 5,464,911.

One drawback to many stain resist polymer treatments is the tendency of the treated fibers to yellow. This is believed to be the result of photooxidation to quinones of hydroxy-containing aromatic moieties in the stain resist. This yellowing is sufficiently pronounced that it makes certain stain resist treatments commercially unacceptable, and has resulted in numerous attempts to avoid the yellowing problem, such as by applying a phenol-formaldehyde condensation polymer at low pH.

Another drawback to many stain resist compositions is the tendency of the stain resist polymer to wash off of the fabric over time, rendering the carpet again susceptible to staining.

Traditional methods for treating fibers and fabrics, in particular carpet fibers and fabrics, has been to first dye the fiber or fabric, then apply a stain resist, and then apply a soil resist, such as a fluoropolymer. Conventional wisdom has been that the cationic fluoropolymer can damage the stain resist abilities of the anionic stain resist polymer, and thus that these treatments should not be used together. Accordingly, there is a need in the art for an anionic stain resist that can function effectively in the presence of a cationic fluoropolymer soil resist, and that can, if desired, be applied in the dyebath.

It is an object of the present invention to provide a stain resist composition that provides good resistance to staining. It is another object of the invention to provide a stain resist composition that is essentially colorless or that imparts little or no color to the fabric to which it is applied.

It is another object of the present invention to provide a stain resist composition that is associated with no or decreased yellowing of the fibers or fabric treated with the stain resist upon exposure to light. It is another object of the present invention to provide a stain resist composition that is durable, and that passes commonly accepted tests for stain resist durability.

It is a further object of the invention to provide a stain resist composition that can be applied in the dye bath without interfering with the dyeing process, and if possible enhancing the dyeing results. It is a further object of the present invention to provide a stain resist composition that is compatible with, and relatively unaffected by, soil resist compositions, such as anionic and cationic fluoropolymers. SUMMARY OF THE INVENTION

These and other objects and advantages are achieved by the polymers according to the present invention, stain resist compositions containing these polymers, and fibers treated with the stain resist compositions of the present invention, and by the methods of making and using these polymers, stain resist compositions, and treated fibers, which also form a part of the present invention. The stain resist polymers, compositions and methods of the invention are applicable to polyamide-containing fibers, such as nylon, wool, and silk.

In one embodiment, the present invention relates to a polymer prepared by mixing a resol polymer or resin and itaconic acid in the presence of a free radical initiator, such as ammonium persulfate or an azo compound. A variety of different resol polymers or resins may be used in the present invention. Diarylsulfone containing resols, sulfonated resols, or sulfonated diarylsulfone containing resols have been found to be particularly suitable. In particular, sulfonated resol resins obtained by polymerizing hydroxy- substituted diarylsulfones with formaldehyde at moderate temperatures in the presence of strong base have been found to be suitable. The resulting polymer can be obtained as a suspension in water, and can be diluted in water and applied to fabric or fibers in a manner conventional for applying stain resist compositions. As described in more detail below, the stain resist compositions according to the present invention can also be exhausted onto fibers or fabric in the dyebath.

While not wishing to be bound by any theories, it is believed that at least some of the available hydroxy moieties of the resol polymer may react to form a covalent bond, e.g., with the itaconic acid, or are oxidized. The polymers of the invention generally have a molecular weight ranging from about 750 to about 8500. One possibility is that one or both of the acid moieties of the itaconic acid reacts with one or two hydroxy moieties on the resol polymer to form an ester linkage. The itaconic acid may similarly react with other resol polymer chains, in effect crosslinking the resol. The itaconic acid may also polymerize, forming a polyitaconic acid chain that is, in effect, grafted onto the resol polymer. A combination of these two mechanisms may also occur. Alternatively, or in addition, polymer chains containing polymerized itaconic acid and/or resol polymer may form one or more interpenetrating polymer networks (IPN), and these IPNs may entrain, entangle, crosslink, or otherwise react or associate with other polymers, oligomers, or small molecules, such as sodium xylene sulfonate. It is also possible that the unsaturated portion of the itaconic acid reacts with the hydroxy moieties of the resol polymer to form a 1,2-dicarboxypropylene moiety. The carboxy groups may be neutralized with an aqueous base, forming the corresponding acid salts. It is believed that when the stain resist polymer of the present invention is applied to fibers capable of bonding to anionic dyes or staining materials, the anionic carboxylate moieties tie up many or all of the available bonding sites. In addition, the abundant anionic charge provided by the free carboxylate moieties of the bound itaconic acid creates good electrostatic repulsion against anionic staining materials, keeping them away from the fiber surface. The sealing effect of the polymer or resin film helps to prevent penetration of dyes and staining materials into the fiber interior. The polymer of the present invention is superior to novolac resins as a stain resist component of stain resist compositions because it imparts to the fiber better protection against staining materials. It is believed that the increased number of hydroxy moieties present in a resol polymer (due to the increased number of methylol groups) provides more numerous sites for reaction with itaconic acid than are available in a novolac polymer, thereby providing additional anionic pendant groups capable of shielding the fiber from attack by staining materials.

In another embodiment of the invention, the polymer of the present invention is prepared by mixing and reacting one or more resol polymer or resin, itaconic acid, and an acrylate, such as hydroxypropylacrylate, desirably in the presence of a free radical initiator, such as ammonium persulfate and/or aromatic sulfonic acids or salts thereof. It has been found that a stain resist polymer, formed from the combination of one or more resol polymers, itaconic acid, and an acrylate, such as hydroxypropyl acrylate, provides extremely long lasting stain resistance, and resistance to even prolonged exposure to staining materials, for example resisting staining with Kool-Aid even during exposure lasting at least 24 hours.

In yet another embodiment of the present invention, the polymer comprises a reaction product of one or more resol polymers and an acrylate, such as hydroxypropyl acrylate in the presence of an initiator, which may be a free radical initiator or a redox initiator. This polymer also provides excellent stain resistance and resistance to soiling.

The present invention also provides a stain resist coating that exhibits substantially decreased yellowing as compared to stain resists containing other polymers, including novolacs. This decreased yellowing is in part due to the decreased yellow color of the stain resist composition itself, and also due to its stability on exposure to light. While again not wishing to be bound by any theory, this is believed to be due to the stabilization of the aromatic ring by reaction of the phenolic hydroxy groups with itaconic acid moieties. This makes ring oxidation to a quinone much more difficult and less likely, thereby substantially decreasing the yellowing noted with other stain resist compositions. The danger of yellowing, thought to result from ultraviolet light and oxidation of available hydroxy moieties in the resol to quinones, is minimized by protection of the hydroxyls as the result of reaction with the itaconic acid. Thus, the present invention allows the use of a type of phenol-formaldehyde condensation polymer that might previously have been avoided in stain resist compositions in favor of novolac polymers due to fear that the higher hydroxy content of a resol polymer would result in more yellowing.

The present invention also relates to stain resist compositions containing the polymers described herein, to fibers and fabrics that have been treated with the stain resist composition, and to methods of making the stain resist and of applying it to fibers and fabrics.

The stain resist compositions of the present invention are also advantageous because they can be applied before dyeing, after dyeing, or in the dyebath. Again, not wishing to be bound by any theory, it is believed that the abundant carboxylate groups resulting from the itaconic acid derived pendant groups are sufficient to protect cationic dyesites on the fabric from staining by anionic dyes or staining materials.

Finally, the stain resist of the present invention is completely compatible with fluoropolymeric soil resist agents, since the abundant anionic sites on the stain resist polymer allow the cationic soil resist agent to closely associate and ionically bond to the stain resist coating without affecting the ionic bond of the stain resist to the cationic sites on the fiber.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention can be more clearly understood by reference to the drawings, described below, which are not intended to limit the scope of the claims.

FIG. 1 is a graph showing the proton nuclear magnet resonance spectrum of a stain resist polymer according to the present invention.

1

FIG. 2 is a graph showing the C nuclear magnet resonance spectrum of a stain resist polymer according to the present invention.

FIG. 3 is a graph showing the results of gel permeation chromatography with UV detection of a stain resist polymer according to the present invention.

FIG. 4 is a graph showing the results of gel permeation chromatography with UV detection of a stain resist polymer according to the present invention prepared without the presence of sodium xylene sulfonate.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

As used herein, the term "resol polymer" refers to any base-catalyzed phenol- formaldehyde condensation polymer. The term "itaconic acid" as used herein to refer to the polymer of the present invention refers itaconic acid per se (e.g., as a reactant in a process for preparing the polymer and stain resist composition of the invention) and also to the moiety or moieties that form when itaconic acid reacts with the resol resin, including, for example, esterified itaconic acid moieties, 1 ,2-dicarboxylpropylene moieties and salts thereof, polyitaconic acid domains.

The term "polymer" as used herein in connection with novolacs and resols is generally used to denote the novolac or resol before curing. The term "resin" in the same connection is used to denote the novolac or resol after condensation.

The term "monomer" as used herein refers to the chemical species polymerized to obtain a polymer. The term "monomer unit" as used herein refers to the repeating or "mer" units of the condensed polymer.

Itaconic acid can be reacted with any number of different resol polymers within the scope of the present invention. All that is necessary is that the resol polymer be the base-catalyzed condensation product of a phenol (which may be optionally substituted by any moiety that will not interfere in the resol condensation) and formaldehyde.

Resols that contain sulfoxy moieties have been found to be particularly suitable. For instance, this sulfoxy-containing resol may contain one or more repeating units of a diarylsulfone moiety, e.g., a resol prepared by condensing formaldehyde with a dihydroxydiphenylsulfone. These diarylsulfone moieties may contain further substitution, e.g., by sulfonic acid moieties, carboxylic acid moieties, derivatives thereof, or mixtures thereof. Another sulfoxy-containing resol suitable for the invention is a resol containing repeating units of a phenol or naphthol substituted with sulfonic acid or derivatives thereof. A particularly suitable resol includes both diarylsulfone and hydroxyarylsulfonic acid moieties.

It is expected that the products of the reaction of itaconic acid with a resol polymer according to the present invention might include esters formed by the hydroxy moieties of the resol polymer with the itaconic acid carboxyl groups, ethers formed by reaction of the hydroxy moieties with the unsaturated portions of the itaconic acid, or simple blends of the resol with polyitaconic acid. One or more of these materials, or additional, completely different materials, might be present in the reaction product of the present invention. The itaconic acid may function to crosslink the resol polymer, or to simply anchor to the resol domains of polyitaconic acid, or to simply increase the molecular weight of the mixture by forming a blend of polymers or an interpenetrating polymer network. In any case, the resulting reaction product can be used to form a stain resist composition with superior resistance to anionic staining materials, decreased color and yellowing on exposure to light, suitability for exhaustion in dyebaths, and compatibility with fluoropolymer soil resistant coatings.

The polymer of the present invention can be prepared by combining a resol polymer with itaconic acid at a ratio of between about 10 mole% and about 200 mole%, based upon the free hydroxyl moieties in the unreacted resol, water, and a free radical catalyst, such as ammonium persulfate, 2,2'-azobis(2-amidinopropane) dihydrochloride, or 4,4'-azobis(4-cyanopentanoic acid) in an amount ranging from about 0.5 mole% to about 25 mole%, based on the free hydroxyl moieties. This mixture is reacted by heating to a temperature of about 70 °C to about 110 °C for a time period ranging from about 30 min. to about 300 min. The reaction mixture is then cooled, and a mixture of strong alkali, such as sodium hydroxide, and water are added to the reactor in order to stabilize the reaction at room temperature.

The resol polymers used in the present invention can be prepared using reactants, catalysts, and processes that are known or available in the art. In general, a phenolic compound is reacted with a stoichiometric excess of a form or source of formaldehyde, such as paraformaldehyde, in the presence of aqueous alkaline at a temperature ranging from about 80 °C to about 170 °C. To prepare sulfonated resol polymers, a sulfonating agent, such as phenol sulfonic acid, may also be added to the reaction mixture. The acidic nature of such a reactant may require additional alkali over what would normally be necessary to prepare a resol without the sulfonating agent, due to neutralization by the acidic sulfonic acid groups. When diarylsulfone-containing resols are desired, they can be prepared by using a hydroxy-substituted diarylsulfone, more particularly a dihydroxydiarylsulfone, as the phenolic compound. Hydroxy-substituted diarylsulfones are available in the marketplace, and their synthesis is known in the art. Sulfonic acid substituted resols can also be prepared by condensing hydroxyphenylsulfonic acid with the formaldehyde source. Resols having more than one phenolic moiety can be prepared by condensing different starting materials with the formaldehyde source.

The polymer of the present invention, obtained by reacting the resol polymer with itaconic acid under the conditions described above, can be applied to fabrics or fibers by forming it into a stain resist composition. This is typically done by dissolving the polymer, which may be in the form of a solution, into water at a concentration ranging from about 2.0 g/L to about 60 g/L. The pH of this solution can be adjusted to a pH of about 1.8 to about 2.5 using pH adjustment agents such as A-80 urea sulfate from Peach State Labs. Other components may also be added to the stain resist composition, such as nonionic or anionic detergents, antistatic agents, dyestuffs, ultraviolet absorbers, antioxidants, antimicrobials, and fluoropolymer soil resist compounds.

The fiber or fabric is then immersed in this solution for sufficient time for the fiber for fabric to be completely wetted and/or soak up the solution, typically about 0.02 to about 10 mins. The fabric is then heated to a temperature in the range of about 25 °C to about 100 °C, more particularly heating to about 100 °C. The fabric is then rinsed and dried at temperatures ranging from about 60 °C to about 125 °C until dry.

The treated fabric will then be resistant to stains, and this stain resist property is quite durable, withstanding repeated washings or shampooings, even with strong, alkaline detergents. The fibers and fabrics treated with the stain resist composition of the present invention can be further treated with fluoropolymer soil resist compounds in order to decrease the wettability of the fibers or fabrics, and to prevent soiling. The stain resist polymers and compositions of the present invention are fully compatible with cationic fluoropolymer soil resist compounds, and the latter can be applied to fibers and fabrics treated in accordance with the present invention using spraying, foaming, padding, or exhausting techniques known to those of skill in the art of soil resists. The present invention is effective when applied in this manner, in stark contrast to currently available stain resists, which are noticeably ineffective when a cationic fluoropolymer is used by any means of application. In an alternative embodiment of the present invention, the stain resistant polymer comprises the reaction product of a resol polymer, itaconic acid, and an acrylate, in particular hydroxypropyl acrylate, in the presence of the free radical initiators described above. While not wishing to be bound by any theory, it is believed that the presence of the acrylate beneficially affects the hydrophobic nature of the polymer. Moreover, hydroxy-substituted acrylates are believed to confer additional advantages by virtue of their hydroxy functional groups, which may include increased hydrogen bonding to the fiber and possible crosslinking or bonding during heating and drying operations normally carried out during carpet production. At any rate, the use of acrylate esters as monomers in formation of the stain resist polymer, such as hydroxypropyl acrylate, significantly increases the stain resistant nature of the polymer, allowing fiber treated with it to maintain its stain resistance even after prolonged exposure to staining materials. For example, stain resist polymers according to this embodiment of the invention retain are resistant to staining by long-term exposure to Kool-Aid (over a period of at least 24 hours).

The stain resist polymer prepared according to this embodiment of the invention can be used directly, or can be incorporated into a stain resist composition, in particular to decrease the yellowing characteristics of other, less expensive stain resist materials, such as resol polymers. In these situations, other components, such as hydrotropes, surfactants, leveling agents, UV absorbers, antioxidants, and other additives may be included in the composition.

In yet another embodiment of the present invention, the polymer can be prepared by reacting one or more resol polymers with an acrylate, such as hydroxypropyl acrylate, without the presence of itaconic acid, in the presence of a free radical initiator, desirably in the presence of sodium xylene sulfonate. The resulting polymer can be used directly as a stain resist treatment, or can be diluted or combined with other components as described above for other embodiments of the invention. The present invention can be more clearly understood by reference to the following examples, which are not intended or to be interpreted as limiting the scope of the present invention.

EXAMPLES Example 1 - Preparation of Resol Polymer

The reagents listed below were introduced in order into a pressure reactor at ambient temperature, and the temperature increase resulting from the exothermic reaction between the NaOH and PSA controlled during addition to below about 60 °C with vigorous agitation. Weight percentages are based on the total reaction mixture.

The reactor was sealed, and the temperature slowly increased to 140 °C. This was accompanied by an increase in pressure to about 40 - 60 psi. The reactor was maintained at 140 °C for about 7 hours, and then cooled to 50 °C. The mixture was sampled for formaldehyde content, which was typically found to be between 0 and 25 ppm. 37% hydrogen peroxide was then slowly added to the mixture in an amount that is about 1.0 wt%, based on the weight of the reaction mixture. The amount of peroxide should be sufficient to convert 3265 ppm of formaldehyde to formic acid. The resulting mixture was agitated for 30 minutes at 50 °C, and again sampled for formaldehyde, which was typically around 0 ppm. The resulting resol was then removed from the reactor. Its physical properties are given below. pH 6.7 ± 0.2

Density 1.14 g/ml

Viscosity 425 @ 25 °C (LVF #2)

Color amber

Odor mildly phenolic

Example 2 - Preparation of Stain Resist Polymer

The following materials were introduced in order into a reactor under agitation. The resol used was that obtained from Example 1. The itaconic acid is added gradually over the course of the entire addition of other components, and with stirring. Weight percentages are based on the total reaction mixture.

The temperature of the reaction was raised to 95 °C and held at this temperature for 2 hours. It was then cooled to 65 °C and a mixture of water and NaOH in the amounts give below was slowly added.

The resulting mixture was agitated for 30 minutes. Samples were analyzed by GPC and UV/VIS spectrophotometer. The GPC was carried out on a 1% sample in distilled water using a PL Aquagel OH 40 column, an eluant of 0.01 M NaH₂PO₄ at a pH of 7.10, at a flow rate of 1.5 mL/min. The detector was an ultraviolet detector at 254 nm with a range of 0.5. The product was removed from the reactor, and had a pH of 4.00 ± 0.2, had an amber color, and a mildly phenolic odor. The proton and C nmr spectra of this product are given in FIG. 1 and 2, respectively.

Example 3 - Application of Stain Resist Composition

A stain resist bath was prepared by dissolving 8 g/L of the stain resist polymer prepared according to Example 2 into water. The pH of the stain resist bath was adjusted to 2.0 with A-80 urea sulfate. Samples of nylon carpet or knitted nylon tube were weighed, dampened, and excess water extracted. 350 wt% of the stain resist bath, based on the weight of the nylon carpet or knitted nylon tube, was applied to the sample. The sample was submerged in the stain resist bath until evenly saturated. The sample was removed from the bath and steamed for about 2.0 minutes. The sample was then cooled in cold water, and excess water extracted. The treated sample was then allowed to dry completely using hot air and tested for stain resistance and yellowing.

Example 4 - Stain Resistance Testing

The carpet samples and knitted tube samples prepared in Example 3 were subjected to a Quick Stain Test in order to assess whether stain resist application was adequate.

Procedure:

1. Specimens of nylon carpet or knitted nylon tube prepared in Example 3 were cut into approximately 4 cm X 10 cm pieces.

2. 45 g ± 1 g of cherry flavored, sugar presweetened Kool-Aid was dissolved in 500 cc of room temperature water.

3. The Kool-Aid solution was placed in a beaker and its temperature adjusted to 70 °C. 4. The specimens were dipped into the staining solution for 1.0 min. Fresh staining solution was used each time, and only one specimen was dipped into a single beaker.

5. The specimens were removed from the solution, rinsed thoroughly under cool tap water. A centrifugal extractor was used to remove the rinse solution. The samples were evaluated for stain resistance by viewing and evaluating them by comparison to an AATCC Evaluation Red 40 Stain Scale, which can be obtained through the American Association of Textile Chemists and Colorists,. On a scale of 1 to 10, with ten being the best rating, the treated samples had ratings of 9 to 10. The control samples, which were not treated, had ratings of 1 to 2. The specimens prepared according to Example 3 exhibited good stain resistance, while the untreated samples were noticeably stained.

Example 5 - Evaluation of Yellowing

Treated samples were exposed to xenon light for 20 AATCC Fading Units (AFU) and compared to untreated samples. Sample shade change was rated based on the AATCC gray scale of 1 to 5, with 5 corresponding to no change in shade. Treated exposed samples had ratings of 4 to 5. Untreated controls had ratings of 5.

Example 6 - Evaluation of Durability of Stain Resist

Predyed carpet samples made from nylon 6 and nylon 66 were treated with the stain resist composition of Example 2 at 2.8% owg. via a Kusters Fluidye applicator. The stain resist solution, having a concentration of 8 g/L, was adjusted to pH 2.0 with A-80 urea sulfate. The treated samples were then steamed in a vertical carpet steamer for 4.0 min., rinsed, and the rinse solution extracted. The carpet was then treated with an anionic/cationic fluoropolymer blend using a Kusters Flexnip applicator at a pH of 2.0. The fluoropolymer treated carpet was then steamed in the vertical carpet steamer for 1.0 min., rinsed, the rinse solution extracted, and the carpet samples dried at 235 °F. The durability of the stain resist carpet samples above was tested using a detergent wash test known in the art as the WAQE test. The purpose of the test is to compare the stain resistance of fibers or fabric that has been washed using a high pH surfactant with that of unwashed fiber or fabric, thereby simulating the effect of numerous carpet shampooings.

Equipment and Reagents:

1. Detergent Solution:

2.0 ± 0.2 oz. DuPonol® WAQE (DuPont) surfactant is added to 1 gal. water. pH was adjusted to 10.0 ± 0.2 with 0.2% Trisodium phosphate. The detergent solution was allowed to reach room temperature (75 °F ± 5 °F) before using.

2. Staining Agent:

45 g ± 1 g of cherry flavored, sugar presweetened Kool-Aid was dissolved in 500 cc of room temperature water. 3. Wash Container:

A bucket or tray large enough to fully immerse at least one specimen was used. 4. Cylinder:

A polypropylene cylinder of 1.5 to 2 in. diameter was used to confine the stain solution.

Test Procedure

1. 2 specimens of approximate dimensions 6 in. X 6 in. were cut from nylon carpet and knitted tubes that were treated with the stain resist composition of the present invention as described in Example 3. 2. One of the specimens was completely immersed in the wash bucket in the

WAQE prepared as described above for 5 minutes.

3. The specimen was removed from the wash bucket and promptly rinsed under a faucet. Excess solution was removed using an extractor.

4. Detergent solution is replaced after each wash cycle. 5. Staining the specimens: a. The dry, unwashed and washed specimens are placed on a flat nonabsorbent surface. b. 20 mL of Kool-Aid staining solution was poured on each specimen through the cylinder to form a 1.5 to 2 inch circular stain. c. The staining solution was worked into the fibers without abrading them, and the cylinder was removed. d. The samples were left undisturbed for 24 hours ± 4 hours. e. The samples were rinsed thoroughly with cool tap water, squeezed dry, and excess solution removed with an extractor. f. The samples were dried for 5 min. at 180 °F in a dry box. Grading

Specimens are evaluated for staining using the STAINMASTER (Dupont) stain rating scale, i.e., the AATCC RED 40 STAIN SCALE, as described above. The samples described above withstood three WAQE wash cycles without significant staining. The washed and unwashed carpet samples were tested for fluorine via the combustion method to assess the amount of fluoropolymer stain resist remaining thereon. The samples subjected to 3 WAQE cycles retained 60 - 70 % fluorine as compared to the unwashed samples. This indicated that the stain resist composition of the present invention provided superior retention of fluoropolymer soil resist agents, even after numerous harsh washing cycles.

Example 7

A) Preparation of Resol Itaconate Ester The components shown below were mixed and dried at 140°C to promote esterification of the resol hydroxyl moieties by itaconic acid:

Resol of Example 1 : 85.0 wt%

Itaconic acid 14.5 wt% p-TSA 0.5 wt% B) Polymerization of Resol Itaconate Ester

The unsaturated itaconate ester was then dispersed in water as indicated below and heated in the presence of ammonium persulfate to polymerize it.

Product of step A) 17.16 wt%

Water 79.84 wt%

Ammonium persulfate 3.00 wt%

This mixture was heated to a temperature of 85 °C and held at this temperature for 1 hour. The resulting product was then applied to carpet samples in the manner described in Example 3.

Example 8

The samples prepared in Example 7 were tested for staining and yellowing on exposure to light.

The samples prepared by this process were exposed to 160 °F Kool-Aid solution for 1.0 min. and rinsed. The exposed and rinsed samples were rated 9-10 for staining based on the AATCC Red 40 Stain Scale.

The samples were also exposed to xenon light for 20 AATCC Fading Units (AFU). The exposed samples were rated 4-5 for color change on the AATCC gray scale, as compared to the unexposed samples.

Example 9

Undyed carpet made from nylon 66 was dyed and stain treated in the same bath. The dye/stain resist bath consisted of 8 g/L of the stain resist composition of Example 2, 0.5 g/L dioctylsulfosuccinate, 0.25 g/L defoamer, 4.0 g/L A-80 urea sulfate (to adjust the pH of the bath to 2.0), and 0.2 g/L C. I. Acid Blue 324. The dye/resist bath was then applied at 350 % wet pickup based on the carpet weight using a Kuster Fluidye applicator. The treated caφet was then steamed at 212 °F for 4.0 minutes in a continuous vertical caφet steamer. The caφet was then rinsed, and excess rinse solution extracted. The dyed and stain resist treated caφet was then treated with an anionic/cationic fluoropolymer using a Kuster Flexnip applicator. The fluoropolymer bath consisted of 3 g/L of a proprietary anionic/cationic fluoropolymer produced by Peach State Labs, and 2.5 g/L of A-80 urea sulfate (to adjust the pH to 2.0). The fluoropolymer treated caφet was then steamed at 212 °F for 1.0 min. in a continuous vertical caφet steamer, then rinsed and extracted, then dried at 235 °F.

Example 10 Preparation of Resol-itaconic acid-hydroxypropylacrylate stain resist polymer

Mixture A

The reagents listed below were introduced into a reactor and heated to 85 °C, at which time 1% ammonium persulfate was added to the mixture. Resol 1 is the resol polymer prepared in Example 1. Resol 2 is a resol polymer very similar to Resol 1, but is prepared using a slightly larger quantity of paraformaldehyde as indicated below, to increase the molecular weight of the polymer.

These components are reacted and reach a higher degree of condensation due to the 10% increase in paraformaldehyde. The condensation product is then reacted with 1 % (based on the weight of the reaction mixture) of 37% hydrogen peroxide to convert any free formaldehyde. The resulting product is extremely viscous, and is thus diluted with 40 % sodium xylene sulfonate to form a mixture of 80 wt% condensation product and 20 wt% sodium xylene sulfonate. The resulting diluted material is used as Resol 2 below.

Both polymers are used to provide a more desirable molecular weight distribution (for use with both Type 6 and Type 6,6 nylon) than is obtainable from a single resol polymer.

Heating was continued to 95-98°C, and the reaction exotherm controlled with cooling so that the temperature did not exceed 98°C. Cooling is begun when the reaction mixture has been above 80 °C for 1 hour. The resulting polymer is a clear, amber, homogeneous liquid, and can be applied directly to fabric or caφet, or incoφorated with other components into a stain resistant composition.

The resulting polymer material was found to have a weight average molecular weight of around 3800 and a number average molecular weight of around 1250. Gel permeation chromatography with UV detection was performed using a Bio-Rad Model 2700 Solvent Delivery System and a Bio-Dimension™ UV/vis Monitor Model 0206- 9049. The resulting chromatography is shown in FIG. 3. Example 1 1 Preparation of Stain Resist Composition

In order to prepare a more economical stain resist composition, the stain resistant polymer of Example 10 (Mixture A) is combined with unreacted resol polymers (Resols 1 and 2). Because of the unreacted nature of these resols, antioxidants and UV absorbers are also added. MIXTURE B

The resulting composition is also a clear, amber, homogeneous liquid.

Example 12 Application and Testing of Stain Resist Composition

2.67 % owg of Mixture B in Example 11 was introduced into a stain resist bath and applied to Bealieu Type 6 nylon filament fiber using the procedures of Example 3.

Stain resist testing was carried out by soaking the treated samples in double strength (1 package in 1 quart water; single strength Kool-Aid was used in Example 4) cherry flavored, sugar presweetened Kool-Aid at 140 °F for 1 min., followed by rinsing, squeezing out excess Kool-Aid, and drying. The samples had an AATCC Red Food Stain rating of 9, on a scale of 1 to 10, with 10 the highest score. Example 13 Application and Testing of Stain Resist Composition

1.5 % owg of Mixture B in Example 11 was introduced into a stain resist bath and applied to Allied Type 6 nylon filament fiber, using the procedure described in Example 3. Stain resist testing was carried out using the procedures of Example 4 with half strength (1 package in 4 quarts water) cherry flavored, sugar presweetened Kool-Aid at 120 °F for 1 min., followed by rinsing, squeezing, and drying. The samples had an AATCC Red Food Stain rating of 9, on a scale of 1 to 10, with 10 the highest score.

Example 14 Application and Testing of Stain Resist Composition

1.5 % owg of Mixture B in Example 11 was introduced into a stain resist bath and applied to Allied Type 6 nylon spun fiber, using the procedure described in Example 3.

Stain resist testing was carried out using the procedures of Example 4 with double strength (1 package in 1 quart water) cherry flavored, sugar presweetened Kool-Aid at 140 °F for 1 min., followed by rinsing, squeezing, and drying. The samples had an AATCC Red Food Stain rating of 9, on a scale of 1 to 10, with 10 the highest score.

Example 15 Application and Testing of Stain Resist Composition

1.5 % owg of Mixture B in Example 11 was introduced into a stain resist bath and applied to Solutia Type 6,6 nylon spun fiber, using the procedure described in Example 3.

Stain resist testing was carried out using single strength (1 package in 2 quarts water) cherry flavored, sugar presweetened Kool-Aid at 72 °F for 24 hr., followed by rinsing, squeezing, and drying. The samples had an AATCC Red Food Stain rating of 9, on a scale of 1 to 10, with 10 the highest score. Example 16 Application and Light Fastness Testing of Stain Resist Composition

3.0 % owg of Mixture B in Example 11 was introduced into a stain resist bath and applied to Bealieu Type 6 nylon filament fiber, using the procedure described in Example 3.

The samples were exposed to xenon light for 40 AATCC fading units (AFU), and were rated 4-5 for color change on the AATCC gray scale, as compared to unexposed samples. Ratings above 4 are generally considered acceptable for color change, and ratings of 5 are essentially unchanged.

The samples prepared according to Example 15 were also evaluated for 40 AATCC fading units, and were rated at 4-5.

The samples were also subjected to 1 cycle of "burnt gas fumes" testing, where they are exposed to nitrous and various other oxides sufficient to yellow any phenolic compounds, and their color change rated 5 on the AATCC gray scale, as compared to unexposed samples.

Example 17 Resol-hydroxypropyl acrylate polymer

The reagents listed below were combined into a reactor, with ammonium persulfate and sodium metabisulfite added as dose additions to provide a redox initiator.

The resulting polymer was a clear, amber, homogeneous liquid. Example 18 Soil and Stain Resistance Testing

The polymer obtained in Example 17 was applied to Type 6,6 Nylon fiber caφet at a rate of 1.8 % owg, together with 0.19 % owg or 0.57 % owg of a fluorocarbon soil resist composition. A commercially available stain resist composition (FX 661, 3M Coφoration) was applied to the same fiber caφet at the same rate in combination with the same soil resist composition. Soil resist was evaluated by spraying a test soil composition on samples of the treated caφet, subjecting the caφet to a specified number of cycles of simulated foot traffic, cleaning the caφet using a standard steam cleaning technique, and subjecting the caφet to additional cycles of simulated foot traffic. After each operation, the appearance of the caφet was evaluated using a spectrophotometer to generate a ΔE value that accounts for changes in color hue, depth, and reflectance. The smaller the ΔE value, the better the soil resistance of the caφet.

Stain resistance was evaluated using a 24 hour exposure to full strength cherry Kool-Aid at 72 °F for caφet samples before and after simulating 5,000 simulated foot traffic cycles, and evaluating according to the AATCC Red Food Stain scale. The results are presented below.

The results show that the polymer composition of Example 17 provides stain resistance results that are equal to, or better than, commercially available stain resist compositions, without appreciable decrease in soil resistance. Example 19

The reagents listed below were introduced into a reactor and heated to 80 °C:

Heating was continued to 85-90 °C, and the reaction exotherm controlled so that the temperature did not exceed 98 °C. Cooling was begun after the reaction mixture had been above 80 °C for about 1 hour. The resulting polymer is a hazy amber homogeneous liquid of pH 5.75. Gel permeation chromatography with UV detection was performed using a Bio-Rad Model 2700 Solvent Delivery System and a Bio-Dimension™ UV/vis Monitor Model 0206-9049. The resulting chromatograph is shown in FIG. 4.

The particular embodiments of the invention having been described above, these are not limiting of the present invention, and those of skill in the art can readily determine that additional embodiments and features of the invention are within the scope of the appended claims and equivalents thereto.

Claims

WHAT IS CLAIMED IS:

1. A polymer comprising the reaction product formed by reacting a mixture comprising a resol polymer and itaconic acid in the presence of a free radical initiator.

2. The polymer according to claim 1 , wherein the resol polymer comprises a sulfoxy- containing resol polymer.

3. The polymer according to claim 2, wherein the sulfoxy-containing resol polymer comprises a diarylsulfone-containing resol polymer.

4. The polymer according to claim 3, wherein the reaction product has a molecular weight in the range of about 750 to about 8500.

5. The polymer according to claim 1 , comprising an ester comprising an acid moiety derived from itaconic acid or an oligomer or polymer thereof and a alcohol moiety derived from the resol polymer.

6. The polymer according to claim 1 , comprising an ether formed between the resol polymer and itaconic acid.

7. The polymer according to claim 1, comprising a blend of the resol polymer and polyitaconic acid.

8. The polymer according to claim 1, wherein the polymer further comprises the reaction product of a resol polymer and hydroxypropyl acrylate in the presence of a free radical initiator.

9. The polymer according to claim 1, wherein the polymer further comprises the reaction product of itaconic acid and hydroxypropyl acrylate in the presence of a free radical initiator.

10. The polymer according to claim 8, wherein the polymer further comprises the reaction product of itaconic acid and hydroxypropyl acrylate in the presence of a free radical initiator.

11. The polymer according to claim 1 , wherein the mixture further comprises an acrylate ester.

12. The polymer according to claim 11, wherein the acrylate ester is hydroxypropyl acrylate.

13. The polymer according to claim 1 , whererin the mixture further comprises an aromatic sulfonic acid or a salt thereof.

14. The polymer according to claim 13, wherein the aromatic sulfonic acid or salt thereof is sodium xylene sulfonate.

15. The polymer according to claim 1 , wherein the polymer forms one or more inte╧åenetrating polymer networks.

16. A stain resist composition comprising the polymer according to claim 1.

17. A stain resist composition comprising a polymer according to claim 5.

18. A stain resist composition comprising a polymer according to claim 6.

19. A stain resist composition comprising a polymer according to claim 7.

20. A stain resist composition comprising a polymer according to claim 8.

21. A stain resist composition comprising a polymer according to claim 9.

22. A stain resist composition comprising a polymer according to claim 10.

23. A stain resist composition comprising a polymer according to claim 11.

24. The stain resist composition according to claim 16, further comprising a nonionic or anionic detergent.

25. The stain resist composition according to claim 16, further comprising an antistatic agent.

26. The stain resist composition according to claim 16, further comprising a dyestuff.

27. The stain resist composition according to claim 26, further comprising a fluoropolymer soil resist compound.

28. The stain resist composition according to claim 23, further comprising one or more unreacted resol polymer.

29. The stain resist composition according to claim 28, further comprising one or more additional additives selected from the group consisting of hydrotropes, surfactants, leveling agents, pH adjusting agents, UV absorbers, and antioxidants.

30. A polymer of a sulfonated resol polymer or resin and itaconic acid, formed by reacting the sulfonated resol polymer with itaconic acid in the presence of an aqueous persulfate, followed by neutralization with aqueous base.

31. The polymer according to claim 30, wherein said aqueous base is sodium hydroxide.

32. The polymer according to claim 30, wherein said sulfonated resol polymer or resin is formed by reacting a dihydroxydiphenylsulfone with phenolsulfonic acid and paraformaldehyde in the presence of aqueous base at a temperature in the range of about 120 ┬░C to about 160 ┬░C.

33. Fiber treated with the stain resist composition according to claim 16.

34. Fiber according to claim 33, wherein said fiber comprises a polyamide fiber.

35. Fiber according to claim 34, wherein said polyamide is nylon.

36. Fiber treated with the stain resist composition according to claim 17.

37. Fiber treated with the stain resist composition according to claim 11.

38. A method of imparting stain resistance to fiber, comprising contacting the fiber with the stain resist composition according to claim 16 for a sufficient time to substantially coat the fiber, and heating the coated fiber under conditions sufficient to cure the polymer.

39. The method according to claim 38, wherein said contacting of said fiber occurs in a dyebath, simultaneously with dyeing of said fiber.

40. The method according to claim 38, further comprising contacting the fiber with a fluoropolymer soil resist composition.

41. A method of imparting stain resistance to fiber, comprising contacting the fiber with the stain resist composition according to claim 11 for a sufficient time to substantially coat the fiber, and heating the coated fiber under conditions sufficient to cure the polymer.

42. A method for preparing the polymer according to claim 1 , comprising: reacting a resol polymer with itaconic acid in the presence of a catalyst at a temperature of from about 25 ┬░C to about 100 ┬░C.

43. The method according to claim 42, wherein the catalyst is a persulfate salt.

44. The method according to claim 43, wherein the persulfate salt is ammonium persulfate.

45. The method according to claim 42, wherein the temperature is about 140 ┬░C.

46. The method according to claim 42, further comprising contacting the polymer with aqueous strong alkali.

47. The method according to claim 46, wherein the aqueous strong alkali is aqueous sodium hydroxide.

48. The method according to claim 42, further comprising reacting the resol polymer and/or the itaconic acid with an acrylate ester.

49. The method according to claim 48, wherein the acrylate ester is hydroxypropyl acrylate.

50. A method of preparing a stain resist resin coating comprising: preparing a polymer according to claim 42; and heating the polymer to a temperature of from about 25 ┬░C to about 100 ┬░C to cure the polymer into a crosslinked solid resin.

51. A polymer comprising the reaction product of one or more resol polymers and an acrylate ester in the presence of an initiator.

52. The polymer according to claim 51 , wherein the acrylate ester is hydroxypropyl acrylate.

53. The polymer according to claim 51 , wherein the initiator is a free radical or redox initiator.

54. A stain resist composition comprising the polymer according to claim 51.

55. Fiber treated with the stain resist composition of claim 54.