CH689367GA3 - Enhancement of stain resistance of polyamide and wool fabrics - Google Patents

Abstract

Method of enhancing soil- and stain-resisting properties of polyamide and wool fabrics comprises applying to the fabric an aq. soln. contg. the condensn. prod. of formaldehyde with bis(hydroxyphenyl)sulphone, phenylsulphonic acid, dihydroxy diphenyl sulphone or benzene sulphonic acid; and at least 1 material from a wax emulsion and a fluorochemical; and an acrylic polymer and copolymers. Also claimed are (i) the aq. soln. for enhancing the soil- and stain-resistant properties of polyamide and wool fabrics; and (ii) fabric having applied thereto the aq. soln.; and (iii) method for enhancing soil- and stain-resistance of polyamide fabric by immersing or totally wetting the fabric with the aq. soln.

Description

The object of the invention is to provide a method for improving the resistance characteristics of polyamide and wool fabrics against soiling and / or stains; to provide compositions useful for imparting stain resistance characteristics to treated fabrics, as well as treated fabrics. The fabrics can be treated during manufacture, cleaning or refurbishment and they can be treated in whole or in part, i.e. only the surface of the fabric will be treated.

A particular object of the invention is to provide a method for improving the resistance properties of polyamide and wool fabrics against soiling and stains, comprising applying to the fabric a solution containing a condensation product of formaldehyde with a compound from the group: bis (hydroxyphenyl) sulfone; phenylsulfonic acid; dihydroxydiphenylsulfone; benzenesulfonic acid; in combination with a fluorinated chemical compound, plus an acrylic polymer or copolymer.

A particular object of the invention is to provide compositions containing, in a variety of combinations, sulfonated phenolic resins; sulfonated aromatics; compounds of sulfonated phenolics and aldehydes; modified wax emulsions; fluorochemicals; acrylics; low molecular weight organic acids.

Generally, the treatment compositions according to the invention are formulated from the following: condensation products of aldehydes with sulfones or aromatic sulfonic acids; non-ionic and anionic fluorocarbons based on water; acrylic copolymers; modified wax emulsions; citric or sulfamic acid; condensation products of formaldehyde with either bis (hydroxyphenyl) sulfone or phenylsulfonic acid; chemical compound fluorinated with acrylic polymers or copolymers, for example a product sold by Dupont under the trade name TEFLON MF; bis (hydroxyphenyl) sulfone.

Preferred phenolic resins; fluorochemicals; acrylic resins, polymers and copolymers; as well as the water repellent products were chosen from the following:

Phenolic resins:

Condensation products of formaldehyde with one of the following compounds: bis (hydroxyphenyl) sulfone, phenylsulfonic acid, 2,2-bis (hydroxyphenyl) propane, bis (hydroxyphenyl) ether, dihydroxydiphenylsulfone or benzenesulfonic acid, the above compounds generally being novolak resins .

Fluorinated chemical compounds:

Poly (vinylidene fluoride), 2-perfluorooctyl ethylacrylate 2-perfluorooctyl acrylate, 2-perfluoroethyl acrylate, poly (tetrafluoroethylene) and mixtures thereof with: methyl methacrylate, butyl methylacrylate, modified wax emulsion , poly- (vinylidene chloride), ethyl methyl acrylate.

Acrylic resin:

Polymer methyl acrylate, copolymer of methyl acrylate or mixtures of the two previous products with butyl methyl acrylate, methyl methacrylate, butyl acrylate, methyl acrylate and ethyl acrylate.

TEFLON MF:

Anionic mixture of fluorinated chemical compounds and polyacrylic.

Wax emulsions:

Paraffinic wax emulsion, microcrystalline wax emulsion, metallized wax emulsion of the aluminum salt / wax emulsion or zirconium salt / wax emulsion, modified fatty amide dispersion, anionic resin wax emulsion such as the emulsion melamine wax.

Both nylon (polyamide) and woolen fabrics are sensitive to stains from natural and artificial colors such as those found in fruit juices, non-alcoholic beverages, tea, coffee, dyes used in cleaning products, etc.

Water repellents and / or oil resistant products have long been used as fabric protectants to prevent spills of liquids from entering fabrics and to prevent dyes from staining fibers. Waterproofing products of this type protect the fabric only as long as the liquid remains spilled on the surface of the waterproofing coating. When the liquid falls from a certain height or is forced into the fabric by any means, the acid dyes will soil the fabric.

Waterproofing and anti-fouling primers may contain fluorocarbons, waxes, silicones, acrylic polymers or combinations of these, but chemical primers of this nature offer little or no protection against warm to hot liquids. Spilled liquids of this type enter the fiber and coloring begins immediately.

The other disadvantages inherent in known waterproofing primers are that they tend to disappear quickly due to wear or to be contaminated with dirt brought by air and / or by contact, which tends to decrease their effectiveness as waterproofing agents. - a problem particularly marked in the case of surfaces covered with carpets subjected to a very important traffic of pedestrians, for example the vestibules and the corridors of the shopping centers.

Chemicals called preservatives are used in the textile industry to prevent dyeing of polyamide and wool fibers during special printing processes. The same type of chemicals have been used for many years to improve the resistance to washing of acid dyes and to prevent them from rubbing off. Among these products are phenolic resins, which in all known processes require temperatures above room temperature to attach to the fabric, but we have found that when an aqueous solution of a condensation product is applied of an aromatic sulfone or sulfonic acid with an aldehyde (i.e. a phenolic resin) to polyamide or wool fibers at a slightly acidic pH, for example at pH 6.5, and even at alkaline pHs as high as 10, and allowed to dry, the resulting fibers will resist acid dyes without any heat fixation. The stain resistant product only needs to penetrate the fabric at a depth exceeding that where the messy substance would not normally be detected when examining the surface of the fabric, for example at a depth of about 30%. the height of the hairs.

Said condensation products are normally dark in color and they tend to discolor fabrics, in particular light-colored fabrics and, moreover, treatment with such condensation products tends to decrease the resistance to light of many acid dyes. used for dyeing both polyamide and woolen fabrics and leaving them rough, that is to say with a hard or felted surface of the treated fabrics. Such a surface of the fabric gets dirty more easily and is more difficult to clean and refurbish.

The commercially available phenolic resins all carry an anionic charge and are incompatible with many nonionic surfactants and / or cationic products. When phenolic resins are mixed with nonionic surfactants in aqueous solution, the ability of phenolic resins to prevent acid dye stains is significantly reduced in a short period of time and when phenolic resins are mixed with cationic products in an aqueous solution, there is an immediate precipitation of the products.

To achieve satisfactory resistance to acid dyes, it is therefore necessary to reduce certain negative effects of the preferred condensation products, which these share with the phenolic resins, in this case poor resistance to light, discoloration of the color. fiber and a rough texture, retaining dirt.

Acrylic polymers have long been used to simultaneously provide textile fabrics with soil release and texture modification properties to the touch, as well as to provide good water repellency.

It has been found that the addition of a white dispersion of acrylic (anionic) polymer to a phenolic resin considerably reduces the discoloration effect of the treated fabric and also significantly softens it, in addition to provide improved soil release properties. It has also been found that the addition of a fluorinated chemical compound improves the water-repellency and oil-repellency, and improves the anti-fouling properties.

TEFLON MF (registered trademark), a product for protecting carpets, is an anionic mixture of fluorinated chemical compound and polyacrylic resin and it has been found that it is compatible with the two phenolic resins according to the invention.

Laboratory tests have shown that the combination of one of our aldehyde condensation products, i.e. a phenolic resin, with TEFLON MF (fluorinated chemical compound plus an acrylic resin), when it is applied to a fabric, increases the resistance against stains of acid dyes, causes little change in texture of the fabric to the touch, has less effect on the resistance to light than simple phenolic resin, provides anti-aging properties. soiling and causes little or no color change compared to phenolic resin alone. In addition, the product is applied at room temperature since it does not require heat setting for the improved properties to manifest.

This mixed product, sold under the trade name BARTEX, when it is simply diluted in water to a pH not exceeding 7 and sprayed on the polyamide or woolen fabric, will provide a woven product which resists dye stains. acid, which is resistant against soiling and which has good water repellency and oil resistance.

A product is also available sold under the trade name of ALGUARD NS, which is a condensation product of formaldehyde with aromatic sulfonic acids, which is compatible with both nonionic and anionic products and which does not lose its properties. anti-stain when kept in solution with non-ionic surfactants for a long period of time. ALGUARD NS allows us to use fluorinated chemical compounds other than TEFLON MF which, until now, was to our knowledge the only anionic fluorinated chemical compound on the market compatible with a phenolic resin. Under these conditions, TEFLON MF has been replaced by a commercially available non-ionic fluorinated chemical compound. This product, identified by our trademark BARTEX A-200, has the following composition: <tb> <TABLE> Columns = 3 <tb> <SEP> Fluorinated chemical compound <SEP> - <SEP> 10-20% <tb> <SEP> Acrylic copolymer <SEP> - <CEL AL = L> 3.0-10% <tb> <SEP> Condensation products of aromatic sulfonic acid <SEP> - <SEP> 3-10% <tb> <SEP> Citric acid <SEP> - <SEP> pH 5 to 6 <tb> <SEP> Water <SEP> - <SEP> 100% complement <tb> </TABLE>

BARTEX A-200 is a concentrate to be diluted in water in a ratio ranging from 1:20 to 1:32 and it is applied to the surface of the fabric.

BARTEX A-200 is a fabric protection agent which has anti-stain and anti-soiling characteristics and is both oil-resistant and water-repellent. It also has good resistance to wet cleaning when it is simply sprayed onto the surface of nylon or woolen fabrics and left to air dry. These characteristics are applied only to the part of the tissue which has been in contact with the treatment solution.

For some manufacturers and cleaners, there is a market for a less expensive stain-free and stain-release product that does not contain fluorinated chemicals and is less persistent than BARTEX A-200. It is applied to nylon and woolen fabrics during the cleaning process and its application does not require additional labor. This product, BARTEX SA (additive for shampooing), is formulated as follows: <tb> <TABLE> Columns = 3 <tb> <SEP> Acrylic polymer <SEP> - <SEP> 10-20% <tb> <SEP> Condensation product aromatic sulfonic acid / aldehyde <SEP> - <SEP> 5-20% <tb> <SEP> Citric acid <SEP> - <SEP> up to pH 6.5 to 7.0 <tb> <CEL AL = L> Water <SEP> - <SEP> 100% complement <tb> </TABLE>

BARTEX SA is a concentrated product and when added to cleaning solutions, it confers anti-stain and soil release properties to nylon and wool fabrics during the cleaning process when applied at pH 10 or lower. The product is normally applied at a concentration ranging from 0.2 to 0.7%, calculated on the weight of the portion of fibers treated. Significant variations in the application rate are due to variations in the depth of penetration into the fabric (for example, from 20% to 100%). Also, the level of stain protection and soil release can vary considerably outside of this range while continuing to provide results that are good to excellent. We have also discovered that it is possible to provide fabrics with anti-stain, anti-soiling and water-repellent properties without using acrylic resins or fluorinated chemical compounds. A typical formulation of our BARTEX WX product would be as follows: <tb> <TABLE> Columns = 2 <tb> <SEP> Condensation product aromatic sulfonic acid / aldehyde <SEP> 5-20% <tb> <SEP> Modified wax emulsion <SEP> 15-40% <tb> <SEP> pH <SEP> 5-6 <tb> <SEP> Water <SEP> 100% complement <tb> </TABLE>

The level of stain and dirt protection required to give acceptable results can also vary considerably depending on the type of nylon (6 or 66), whether or not it is heat fixed, or whether the fabric is oldest boy. Generally speaking, nylon 6 will require 1.5 times the amount of product used for nylon 66, while wool may require up to twice the amount of product needed for nylon 66. But when fabrics receive anti-stain and anti-soiling treatments during manufacturing, they will only need during the subsequent treatment small additional amounts of anti-stain, anti-soiling and soil release products, to replace the treatment products 'origin which will have been removed by cleaning and normal wear and tear.

The products of the invention are essentially intended to be used to increase or supplement the anti-stain, anti-soiling and / or soil release properties of fabrics which have been treated in this way during manufacture and will be used by example during the cleaning process or as a separate surface primer, sprayed after the installation of the manufactured product.

More specifically, the anti-fouling substances reduce the affinity of the tissues for soiling, while the soil-releasing substances facilitate the elimination of soiling.

Also, BARTEX SA can be applied to nylon fibers during the manufacturing process at levels ranging from 1% to 6% of the weight of the fibers, and it will provide excellent stain and soil release properties. In this case, the fabric is immersed in an aqueous solution containing BARTEX SA and it may or may not then receive a fluorinated chemical compound as a spray.

It should be noted that in general, the dyestuffs used as food additives use anionic dyes as substances providing color, and it is these substances which are fixed on the nylon and wool fibers, either chemically or electrostatically. .

The following specific examples will serve to illustrate the invention:

Example 1 - Comparison TEFLON MF, TEFLON MF + phenolic resin, untreated (nylon 66).

Example 2 - Comparison TEFLON MF + phenolic resin, phenolic resin (nylon 66).

Example 3 - Comparison of phenolic resin, phenolic resin + acrylic, acrylic (nylon 66).

Example 4 - TEFLON MF comparison, fluorinated chemical compound + phenolic resin, untreated (nylon 6).

Example 5 - Comparison TEFLON MF + phenolic resin, phenolic resin (nylon 6).

Example 6 - Comparison of phenolic resin, phenolic resin + acrylic, acrylic (nylon 6).

Example 7 - Comparison TEFLON MF + phenolic resin, TEFLON MF, untreated (wool).

Example 8 - Comparison of phenolic resin + acrylic, phenolic resin, reference (nylon 66).

Example 9 - Comparison of phenolic resin + acrylic, phenolic resin, reference (nylon 6).

Example 10 - Comparison of phenolic resin + acrylic pH 10, phenolic resin + acrylic pH 6.5 (nylon 66).

Example 11 - Comparison TEFLON MF + phenolic resin, Bartex A 200 (nylon 66).

Example 12 - Comparison of modified wax emulsion + phenolic resin, phenolic resin, acrylic, reference (nylon 6).

Example 13 - Comparison of modified wax emulsion + phenolic resin, phenolic resin, acrylic, reference (nylon 66).

In each of the examples, the tissue samples which had first been treated with stain / soil release solutions and dried were exposed to a stain test. In some examples, an untreated tissue sample was used as a reference.

In examples 1 to 7, 10, 11, 12 and 13, the following coloring test was used: 20 ml of a sweet and cherry flavored solution KOOL-AID (registered trademark) are poured into a ring of 2 1/4 inch diameter placed on the surface of the mat. The solution is pressed into the carpet and left there for one hour at room temperature. The sample is rinsed under running cold water, dried and evaluated on a scale from 1 to 5, in which 5 represents the complete elimination of the stain. Only the treated part of the hair (approximately 30% of the height of the hair) was assessed for stain resistance.

In the examples, a scale from 1 to 5 was used to assess the yellowing, with 5 representing the absence of yellowing and 4 representing an acceptable yellowing.

In the examples, discoloration due to exposure to light was determined using the AATCC test method with an exposure time of 40 hours. The exposed samples were scored using a rating scale from 1 to 5, in which 5 represents the absence of discoloration and a score of 4 is acceptable.

In Examples 8 and 9, the following staining test was used 20 ml of an aqueous solution sweetened and flavored with cherry KOOL-AID are poured into a ring 2 1/2 inches in diameter placed on a carpet surface . The solution is pressed into the mat and left for 8 hours at room temperature (22 degrees C). The sample is rinsed with running cold water, dried and evaluated on a scale from 1 to 5, in which 5 represents a complete removal of the stain.

Example 1 and comparative examples A-1 and B-1

In Example 1, an aqueous solution of TEFLON MF was prepared according to the manufacturer's instructions at room temperature to provide a 6.25% solution. To this solution was added 1% of a 30% by weight solution of phenolic resin, and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 66 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Comparative Example A-1, an aqueous solution of TEFLON MF was prepared at 20 DEG C according to the manufacturer's instructions to obtain a 6.25% solution. This solution was then sprayed onto the surface of an undyed nylon 66 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature (22 DEG C).

In Comparative Example B-1, the undyed nylon 66 carpet was left untreated.

Each sample was tested for initial stain resistance and stain resistance characteristics after extraction cleaning with hot water using 10 g / l of a commercial solution to clean the carpets. <tb> <TABLE> Columns = 3 Table 1 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Stain resistance after cleaning <tb> <SEP> 1 <SEP> 5 <SEP> 4 <tb> <SEP> A-1 <CEL AL = L> 1 <CEL AL = L> 1 <tb> <SEP> B-1 <SEP> 1 <SEP> 1 <tb> </TABLE>

The results of Table 1 show that the treatment of the nylon 66 carpet with TEFLON MF in combination with a phenolic resin provides resistance against stains before and after cleaning the treated part of the fibers and that TEFLON MF alone does not offers initially and after cleaning only negligible resistance against stains.

Example 2 and comparative examples A-2 and B-2

In Example 2, an aqueous solution of TEFLON MF was prepared at 20 DEG according to the manufacturer's instructions to obtain a 6.25% solution. To this solution was added 1% of a 30 percent by weight solution of phenolic resin, and the pH adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 66 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Comparative Example A-2, a 1% aqueous solution of a phenolic resin was prepared at 20 DEG C and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 66 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature (22 DEG C).

Each sample was tested for its original stain resistance and yellowing characteristics. <tb> <TABLE> Columns = 3 Table 2 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Yellowing <tb> <SEP> 2 <SEP> 5 <SEP> 4.5 <tb> <SEP> A-2 <SEP> 5 <SEP> 3 <tb> </TABLE>

The results in Table 2 show that the treatment of the nylon 66 carpet with TEFLON MF in combination with a phenolic resin causes significantly less yellowing of the treated part of the fiber than the sulfonated phenolic resin alone, while continuing to provide excellent stain resistance. Furthermore, the yellowing in Example A-2 is unacceptable, while the yellowing in Example 2 is acceptable.

Example 3 and comparative tests A-3 and B-3

In Example 3, a 1.0% aqueous solution was prepared at 20 DEG C with a 30 percent by weight solution of phenolic resin and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 66 carpet at the rate of 20 ml / square foot, brushed in the bristles and left to air dry for 12 hours at room temperature.

In Example A-3, a 1.0% aqueous solution was prepared with a 30 percent by weight solution of phenolic resin, to this solution was added 2% of a 25 percent aqueous solution hundred weight polyacrylic, and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 66 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Example B-3, a 2% aqueous solution was prepared with a 25 percent by weight aqueous solution of acrylic and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 66 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

Each sample was tested for the initial characteristics of stain resistance and yellowing, and stain resistance after extraction cleaning with hot water using 10 g / l of a commercial solution to clean carpets . <tb> <TABLE> Columns = 4 Table 3 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Resistance against stains after cleaning <tb> Head Col 4: Yellowing <tb> <SEP> 3 <SEP> 5 <SEP> 4 <SEP> 3 <tb> <SEP> A-3 <SEP> 5 <SEP> 4 <CEL AL = L> 4.5 <tb> <SEP> B-3 <SEP> 3 <SEP> 2 <SEP> 5 <tb> </TABLE>

As shown in the results in Table 3, treating nylon 66 with a phenolic resin in combination with a polyacrylic provides generally better results than both the phenolic resin alone and those of the polyacrylics alone. This comparison was carried out on the treated part of the height of the hairs, that is to say approximately 30% of the height of the hairs.

Example 4 and comparative examples A-4 and B-4

In Example 4, an aqueous TEFLON MF solution was prepared according to the manufacturer's instructions at room temperature to obtain a 6.5% solution. To this solution was added 1.5% of a 30% by weight solution of phenolic resin, and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 6 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Comparative Example A-4, an aqueous solution of TEFLON MF was prepared at 20 DEG C according to the manufacturer's instructions, to obtain a 6.5% solution. This solution was then sprayed onto the surface of an undyed nylon 6 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Comparative Example B-4, the undyed nylon 6 carpet was left untreated.

Each sample was tested for initial stain resistance and stain resistance characteristics after extraction cleaning with hot water using 10 g / l of a commercial solution to clean the carpets. <tb> <TABLE> Columns = 3 Table 4 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Stain resistance after cleaning <tb> <SEP> 4 <SEP> 5 <SEP> 4 <tb> <SEP> A-4 <CEL AL = L> 1 <CEL AL = L> 1 <tb> <SEP> B-4 <SEP> 1 <SEP> 1 <tb> </TABLE>

As the results in Table 4 show, treating the nylon 6 carpet with TEFLON MF in combination with a phenolic resin provides resistance against stains before and after cleaning the treated part of the fabric and TEFLON MF alone does not offers negligible resistance against stains before and after cleaning.

Example 5 and comparative examples A-5 and B-5

In Example 5, an aqueous solution of TEFLON MF was prepared at 20 DEG C according to the manufacturer's instructions to obtain a 6.25% solution. To this solution was added 1.5% of a 30% by weight solution of phenolic resin, and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 6 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Comparative Example A-5, a 1.5% aqueous solution of phenolic resin was prepared at 20 DEG C and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 6 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

Each sample was tested for the initial characteristics of stain resistance and yellowing. <tb> <TABLE> Columns = 3 Table 5 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Yellowing <tb> <SEP> 5 <SEP> 5 <SEP> 4.5 <tb> <SEP> A-5 <SEP> 5 <SEP> 3 <tb> </TABLE>

As the results in Table 5 show, treating the nylon 6 carpet with TEFLON MF in combination with a phenolic resin causes significantly less yellowing on the treated part of the fabric than the phenolic resin alone, while continuing to provide excellent resistance against stains. In addition, the yellowing of Example A-5 is unacceptable, while the yellowing of Example 5 is acceptable.

Example 6 and comparative examples A-6 and B-6

In Example 6, a 1.5% aqueous solution of phenolic resin was prepared at 20 DEG C from a 30% by weight solution and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 6 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Example A-6, a 1.5% aqueous solution of phenolic resin was prepared and to this solution was added 2% of a 25 weight percent aqueous solution of polyacrylic and the pH was been adjusted to 6.5. This solution was then sprayed onto the bristles, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to air dry for 12 hours at room temperature.

In Example B-6, a 2% aqueous solution was prepared from a 25 percent by weight aqueous solution of polyacrylic and the pH was adjusted to 6.5. This solution was then sprayed onto an undyed nylon 6 carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at approximately 30% of the bristles height) and left to air dry for 12 hours at room temperature.

Each sample was tested for the initial characteristics of stain resistance and yellowing, and stain resistance after extraction cleaning with hot water using 10 g / l of a commercial solution to clean carpets . <tb> <TABLE> Columns = 4 Table 6 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Resistance against stains after cleaning <tb> Head Col 4: Yellowing <tb> <SEP> 6 <SEP> 5 <SEP> 4 <SEP> 3 <tb> <SEP> A-6 <SEP> 5 <SEP> 4 <CEL AL = L> 4.5 <tb> <SEP> B-6 <SEP> 3 <SEP> 2 <SEP> 5 <tb> </TABLE>

As the results in Table 6 show, the treatment of nylon 66 with phenolic resin in combination with polyacrylic provides better results than those obtained either with phenolic resin alone or with polyacrylic only. This comparison was made on the basis of the treated part of the height of the hairs, that is to say approximately 30% of the height of the hairs.

Example 7 and comparative examples A-7 and B-7

In Example 7, an aqueous solution of TEFLON MF was prepared at 20 DEG C according to the manufacturer's instructions to obtain a 6.5% solution. To this solution was added 2% of a 30 percent by weight solution of a phenolic resin and the pH was adjusted to 6.5 with citric acid. This solution was then sprayed onto the surface of a 100% wool carpet at the rate of 20 ml / square foot, brushed into the bristles (penetration at about 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Comparative Example A-7, an aqueous solution of TEFLON MF was prepared at 20 DEG C according to the manufacturer's instructions to obtain a 6.5% solution. This solution was then sprayed onto the surface of a 100% wool carpet at a rate of 20 ml / square foot, brushed into the bristles (penetration, at about 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Comparative Example B-7, the 100% wool carpet was left untreated.

Each example was tested for the characteristics of initial stain resistance and stain resistance after extraction with hot water using 10 g / l of a commercial solution to clean the carpets. <tb> <TABLE> Columns = 3 Table 7 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Stain resistance after cleaning <tb> <SEP> 7 <SEP> 5 <SEP> 4 <tb> <SEP> A-7 <CEL AL = L> 1 <CEL AL = L> 1 <tb> <SEP> B-7 <SEP> 1 <SEP> 1 <tb> </TABLE>

As the results in Table 7 show, treating a 100% wool carpet with TEFLON MF in combination with a phenolic resin provides stain resistance before and after cleaning, and TEFLON MF by itself only offers '' negligible resistance against stains, before and after cleaning.

Example 8 and comparative examples A-8, B-8 and C-8

In Example 8, a sample of 20 g of carpet was placed in a bath containing 0.5 g of BARTEX SA and 300 g of water, with a pH adjusted to 2.3 with sulfamic acid. undyed nylon 66. The temperature was raised to about 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example A-8, a bath containing 0.5 g of a solution by weight of 30% by weight of phenolic resin and 300 g of water was placed with a pH adjusted to 2.3 with acid. sulfamic, a 20 g sample of undyed nylon 66 carpet. The temperature was raised to about 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example B-8, a bath containing 0.5 g of another phenolic resin at 30% by weight and 300 g of water was placed in a bath, with a pH adjusted to 2.3 with sulfamic acid, a 20 g sample of undyed nylon 66 carpet. The temperature was increased to about 85 DEG C and held for 20 minutes, then the sample was rinsed and dried at 110 DEG C for 15 minutes.

In Comparative Example C-8, a 20 g sample of undyed nylon 66 carpet was placed in a bath containing 300 g of water, with a pH adjusted to 2.3 with sulfamic acid. The temperature was raised to about 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

Each example was tested for the initial characteristics of stain resistance, yellowing and discoloration due to light. <tb> <TABLE> Columns = 4 Table 8 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Yellowing <tb> Head Col 4: Discoloration due in the light <tb> <SEP> 8 <SEP> 4 <SEP> 5 <SEP> 4 <tb> <SEP> A-8 <SEP> 3-4 <SEP> 4 <SEP> 3 <tb> <CEL AL = L> B-8 <SEP> 4-5 <SEP> 4 <SEP> 2 <tb> <SEP> C-8 <SEP> 1 <SEP> 5 <SEP> 5 <tb> </TABLE>

As can be seen in the results in Table 8, Example 8 (acrylic polymer, with phenolic resin) provides average stain resistance compared to that of the two comparative phenolic resin samples, negligible yellowing and acceptable discoloration by light. Conversely, Examples A-8 and B-8 show good resistance to stains, but barely acceptable yellowing and discoloration due to unacceptable light.

Example 9 and comparative examples A-9, B-9 and C-9

In Example 9, a sample of 20 g of carpet was placed in a bath containing 0.9 g of BARTEX SA and 300 g of water, with a pH adjusted to 2.3 with sulfamic acid. undyed nylon 6. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example A-9, we placed in a bath containing 0.9 g of a solution at 30% by weight of phenolic resin and 300 g of water, with a pH adjusted to 2.3 with 1 sulfamic acid, a 20 g sample of undyed nylon 6 carpet. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example B-9, a bath containing 0.5 g of another phenolic resin at 30% by weight and 300 g of water was placed in a bath, with a pH adjusted to 2.3 with sulfamic acid, a 20 g sample of undyed nylon 6 carpet. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example C-9, a 20 g sample of undyed nylon 6 carpet was placed in a bath containing 300 g of water, with a pH adjusted to 2.3 with sulfamic acid. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

Each example was tested for the initial characteristics of stain resistance, yellowing and discoloration due to light. <tb> <TABLE> Columns = 4 Table 9 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Yellowing <tb> Head Col 4: Discoloration due in the light <tb> <SEP> 9 <SEP> 4 <SEP> 4-5 <SEP> 4 <tb> <SEP> A-9 <SEP> 3 <SEP> 4 <SEP> 3 <tb> <CEL AL = L> B-9 <SEP> 4 <SEP> 3 <SEP> 2 <tb> <SEP> C-9 <SEP> 1 <SEP> 5 <SEP> 5 <tb> </TABLE>

As shown by the test results in Table 9, Example 9 (acrylic polymer with phenolic resin) provides above average stain resistance compared to the two comparative samples of phenolic resins, negligible yellowing and acceptable discoloration in the light. Conversely, Examples A-9 and B-9 show marginal resistance against staining, unacceptable discoloration due to light and marginal to unacceptable yellowing.

Example 10 and comparative example A-10

In Example 10, a 1.0% aqueous solution of a 30% by weight solution of phenolic resin was prepared and to this solution was added 2% of a 25% by weight aqueous solution of polyacrylic, 0.1% of a commercial cleaning solution for carpets, and the pH was adjusted to 10. This solution was then sprayed onto the hair of an undyed nylon 66 carpet at a rate of 10 ml / square foot, brushed in the bristles (penetration at approximately 30% of the bristle height) and left to air dry for 12 hours at room temperature.

In Comparative Example A-10 a 1.0% aqueous solution was prepared from a 30% by weight solution of phenolic resin and to this solution was added 2% of a 25% aqueous solution to -center by weight of polyacrylic, 0.1% of a commercial cleaning solution for carpets, and the pH was adjusted to 10. This solution was then sprayed onto the surface of the pile of a non-nylon 66 carpet dyed at the rate of 10 ml / square foot, brushed into the bristles (penetration at approximately 30% of the height of the bristles) and left to air dry for 12 hours at room temperature.

Each example was tested for the characteristics of initial stain resistance and stain resistance after extraction cleaning with hot water using 10 g / l of a commercial solution to clean the carpets. <tb> <TABLE> Columns = 3 Table 10 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Resistance against stains after cleaning <tb> <SEP> 10 <SEP> 4-5 <SEP> 3-4 <tb> <SEP> A-10 <SEP> 5 <SEP> 4 <tb> </TABLE>

As the results in Table 10 show, treating a nylon 66 carpet at a pH level of 10 has a stain resistance that is only slightly lower than that of A-10 treated at a pH level 6.5. The presence of a carpet cleaning solution had no effect on the stain resistance characteristics.

Example 11 and comparative example A-11

In Example 11, an aqueous TEFLON MF solution was prepared at room temperature according to the manufacturer's instructions to obtain a 6.25% solution. To this solution was added 1% of a 30% by weight solution of phenolic resin, and the pH was adjusted to 6.5. This solution was then sprayed onto the surface of an undyed nylon 66 carpet at a rate of 20 ml / square foot, brushed into the bristles (penetration at about 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

In Comparative Example A-11, a 1.5% aqueous solution of BARTEX A200 was prepared at room temperature, with a resulting pH of 6.5. This solution was then sprayed onto the surface of an undyed nylon 66 carpet at a rate of 20 ml / square foot, brushed into the bristles (penetration at about 30% of the height of the bristles) and left to dry with air for 12 hours at room temperature.

Each sample was tested for the characteristics of initial stain resistance and stain resistance after cleaning by extraction with hot water using 10 g / l of a commercial solution for cleaning carpets, yellowing and discoloration due to light. <tb> <TABLE> Columns = 5 Table 11 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Resistance against stains after cleaning <tb> Head Col 4: Yellowing <tb> Head Col 5: Discoloration due in the light <tb> <SEP> 11 <SEP> 5 <SEP> 4 <SEP> 4,5 <SEP> 4 <tb> <SEP> A-11 <SEP> 5 <SEP> 4.5 <CEL AL = L> 4.5 <SEP> 4.5 <tb> </TABLE>

As the results in Table 11 show, treating the nylon 66 carpet with either stain-resistant combination provides excellent results in all tests.

Example 12 and comparative examples A-12, B-12 and C-12

In Example 12, a sample of 20 g of nylon carpet was placed in a bath containing 0.9 g of Bartex WX and 300 g of water, with a pH adjusted to 2.3 with sulfamic acid. 6 undyed. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example A-12, we placed in a bath containing 0.9 g of solution at 30% by weight of phenolic resin and 300 g of water, with a pH adjusted to 2.3 with acid sulfamic, a 20 g sample of undyed nylon 6 carpet. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example B-12, a bath containing 2% of an acrylic resin at 25% by weight and 300 g of water was placed in a bath, with a pH adjusted to 2.3 with sulfamic acid, a 20 g sample of undyed nylon 6 carpet. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example C-12, a sample of 20 g of undyed nylon 6 carpet was placed in a bath containing 300 g of water, with a pH adjusted to 2.3 with sulfamic acid. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

Each example was tested for the initial characteristics of stain resistance, yellowing and discoloration due to light. <tb> <TABLE> Columns = 4 Table 12 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Yellowing <tb> Head Col 4: Discoloration due in the light <tb> <SEP> 12 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> A-12 <SEP> 4 <SEP> 4 <tb> <SEP> B-12 <CEL AL = L> 3 <SEP> 4-5 <SEP> 5 <tb> <SEP> C-12 <SEP> 1 <SEP> 5 <SEP> 5 <tb> </TABLE>

As the results in Table 12 show, the Bartex WX of Example 12 (wax emulsion and phenolic resin) provides excellent resistance against stains compared to phenolic resin alone or acrylic resin alone.

Conversely, Example A-12 shows acceptable stain resistance and yellowing and unacceptable discoloration due to light.

Example B-12 shows acceptable resistance to staining, acceptable yellowing and discoloration due to light.

It is quite evident in Example 12, that Bartex WX is superior to all the other examples.

Example 13 and comparative examples A-13, B-13 and C-13

In Example 13, a sample of 20 g of carpet was placed in a bath containing 0.9 g of Bartex WX and 300 g of water, with a pH adjusted to 2.3 with sulfamic acid. undyed nylon 66. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example A-13, we placed in a bath containing 0.9 g of solution at 30% by weight of phenolic resin and 300 g of water, with a pH adjusted to 2.3 with acid sulfamic, a 20 g sample of undyed nylon 66 carpet. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example B-13, a bath containing 2% of a 25% by weight solution of acrylic resin and 300 g of water was placed in a pH adjusted to 2.3 with acid. sulfamic, a 20 g sample of undyed nylon 66 carpet. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

In Comparative Example C-13, a sample of 20 g of undyed nylon 66 carpet was placed in a bath containing 300 g of water, with a pH adjusted to 2.3 with sulfamic acid. The temperature was increased to 85 DEG C and held for 20 minutes. The sample was rinsed and then dried at 110 DEG C for 15 minutes.

Each example was tested for the initial characteristics of stain resistance, yellowing and discoloration due to light. <tb> <TABLE> Columns = 4 Table 13 <tb> Head Col 1: Example <tb> Head Col 2: Resistance against Tasks <tb> Head Col 3: Yellowing <tb> Head Col 4: Discoloration due in the light <tb> <SEP> 13 <SEP> 5 <SEP> 5 <SEP> 5 <tb> <SEP> A-13 <SEP> 4 <SEP> 4 <SEP> 3 <tb> <CEL AL = L> B-13 <SEP> 3 <SEP> 4-5 <SEP> 5 <tb> <SEP> C-13 <SEP> 1 <SEP> 5 <SEP> 5 <tb> </TABLE>

As the results of the tests in Table 13 show, the Bartex WX of Example 13 (wax emulsion and phenolic resin) provides excellent resistance against stains compared to the phenolic resin alone or the acrylic resin alone.

Conversely, Example A-13 shows acceptable stain resistance and yellowing and unacceptable discoloration due to light.

Example B-13 shows unacceptable stain resistance, acceptable yellowing and discoloration due to light.

It is quite evident from Example 13 that Bartex WX is superior to all the other examples.

The foregoing is given by way of example only and the invention should be limited only by the scope of the appended claims.

Claims (10)

1. A method for increasing the properties of resistance to soiling and to smearing of polyamide and woolen fabrics, characterized in that an aqueous solution containing the condensation product of formaldehyde with a compound chosen from group consisting of bis (hydroxyphenyl) sulfone, phenylsulfonic acid, dihydroxydiphenylsulfone and benzenesulfonic acid and at least one material chosen from the group consisting of a wax emulsion and a fluorochemical product and a polymer chosen from the group formed by an acrylic polymer or copolymer, the aforementioned aqueous solution having a pH of less than 7, and being applied to the tissue by spraying at room temperature and in the absence of any thermal fixation. 2. Method according to claim 1, characterized in that the condensation product is a polymer of benzenesulfonic acid and formaldehyde, the fluorochemical product is a water-based fluorochemical product, nonionic or anionic, the acrylic polymer is polymerized ethyl 2-methylpropenoate and the solution contains citric acid in a proportion sufficient to give it a pH of less than 7. 3. Method according to claim 1, characterized in that the fluorochemical is present in the solution in a proportion which fluctuates from 0.1% to 20%. 4. Method according to claim 3, characterized in that the solution contains 0.1% of fluorochimi product. 5. Aqueous solution to increase the properties of resistance to soiling and to smudging of polyamide and woolen fabrics, characterized in that it comprises, as a mixture, a condensation product of an aromatic sulfonic acid and formaldehyde, in together with a wax emulsion, a water-based, nonionic fluorochemical and an acrylic polymer, the above mixture having a pH of less than 10. 6. Aqueous solution according to claim 5, characterized in that the pH is less than 7. 7. Fibrous material chosen from the group formed by polyamide and woolen fibrous materials, to which a solution containing a polymer of a phenolic compound chosen from the group formed by bis (hydroxyphenyl) sulfone, the acid, has been applied phenylsulfonic, dihydroxydiphenylsulfone and benzenesulfonic acid and an aldehyde, a fluorochemical and an acrylic polymer together with citric acid in a proportion sufficient to give it a pH below 7. 8. Process for increasing the resistance to soiling and to smudging of a polyamide fabric by immersing the fabric in or by completely wetting the fabric with an aqueous solution containing a polymer of a phenolic compound chosen from the group consisting of bis (hydroxyphenyl) sulfone, phenylsulfonic acid, dihydroxydiphenylsulf one and benzenesulfonic acid and an aldehyde, a fluorochemical and an acrylic polymer, the above-mentioned solution having a pH below 7, characterized in that the a hydrophobic and oleophobic fluorochemical product is then sprayed onto the fabric, which also contains an acrylic polymer or copolymer and a phenolic resin. 9. Method for increasing the properties of resistance to soiling and to smearing of polyamide and woolen fabrics, characterized in that an aqueous solution containing the condensation product of formaldehyde and a phenolic compound is applied to the fabric selected from the group consisting of bis (hydroxyphenyl) sulfone, phenylsulfonic acid, dihydroxydiphenylsulfone and benzenesulfonic acid and at least one material selected from the group formed by a wax emulsion and an acrylic polymer, the above aqueous solution having a pH below 7 and being applied to the fabric by spraying at room temperature and in the absence of any thermal fixation. 10. Process for increasing the properties of resistance to soiling and to smearing of polyamide and woolen fabrics, characterized in that an aqueous solution containing the condensation product of formaldehyde and of a selected phenolic compound is applied to the fabric in the group formed by bis (hydroxyphenyl) sulfone, phenylsulfonic acid, dihydroxydiphenylsulfone and benzenesulfonic acid and a wax emulsion, the aqueous solution having a pH below 7 and being applied to the fabric by spraying at room temperature and in the absence of any thermal fixation.