DE69310920T2 - CHEMICAL SYSTEM TO GIVE FIBER MATERIAL STABILITY - Google Patents

Description

The present invention relates to a chemical system for imparting stain resistance to common household stains, in particular to acid dyes, to fibrous materials. Although this system is useful for treating synthetic materials such as nylon, its main application concerns keratinous materials, of which wool is the most important.

Keratinous articles, such as wool carpets, are sensitive to staining by natural and artificial colorants, including acidic colorants commonly found in many foods and beverages. There has long been a need for economical methods to impart stain resistance to these keratinous articles. Particularly desirable are methods that can impart permanent stain resistance to the keratinous articles during conventional processing and treatment steps.

The object of the present invention is to provide a system for the protective treatment of fiber materials, in particular wool carpets, whereby such a system has a reasonable durability during use (dry resistance) and wet cleaning (wet resistance).

The present invention provides a chemical system for imparting stain resistance to common household stains, particularly acidic dyes, to fibrous materials, particularly keratinous materials such as wool fibers used in carpets. The process involves first treating the fibrous material with a mordant. After treatment with the mordant, the fiber is placed in a bath containing a surfactant, a stain inhibitor, a fluorochemical, and, if necessary, an acid to reduce the pH of the bath. A top sealing process to increase the surface protection of the carpet can also be carried out as a final treatment if desired.

The process of the present invention can be applied to undyed fibers or already dyed fibers. If stain resistance is to be imparted to a dyed fiber product by the process of the present invention, the product can be pre-dyed or the mordant can be included in the bath in which the fiber is dyed. Furthermore, the process of the present invention is associated with the dyeing of fabric, can be used with both non-mordant dyes and mordant dyes. The process of the present invention is applicable to both finished and unfinished fabrics.

In the broadest sense, the manufacturing process of wool carpets includes the following steps:

1. Wool is sheared from the sheep and processed in a cleaning bath where the wool is cleaned and bleached, the end product being known as wool fiber base.

2. The fibre base material is cut.

3. The cut fibre base material is carded.

4. The carded wool fibre base material is spun.

5. The spun wool fiber base material is twisted.

6. The twisted wool fiber base material is formed into a strand.

7. The strand is formed into a cone coil.

8. A swelling occurs.

9. The fluffed wool is provided with a backing, creating a wool carpet.

When treating wool as a fiber, the process of the present invention can be applied to the fiber at any suitable stage, e.g. to the original wool fiber stock prior to blending, to the wool skein prior to forming into a cone, or to the bulked wool, in which case a process for continuously dyeing and applying the stain-proofing agent is required.

When the process of the present invention is applied to either the fiber stock prior to cutting or to the wool strand prior to forming into a cone package, and when a dyed final product is required, the process includes the addition of a mordant which is a trivalent mordant such as aluminum sulfate Al₂(SO₄)₃ or aluminum hydroxide Al(OH)₃, or a tetravalent mordant such as zirconium sulfate Zr(SO₄)₂ or zirconium hydroxide Zr(OH)₄, to the normal dye bath (which comprises dye and optionally other suitable adjuvants such as mothproofing agents, leveling agents applied to ensure uniform distribution of the dye throughout the fiber, and the like). The mordant is included in the dye bath in an amount effective to impart greater stain resistance to the fibre than in the absence of mordant, preferably in a weight ratio of 0.5 - 2% based on the weight of fibre in the bath. The bath temperature may be raised to (eg) 80ºC to 98ºC if necessary to allow the fabric to take up the dye. As shown above, the mordant obtained in the first step of the process of the present invention, regardless of whether the dye is a mordant dye or not.

After completion of the dyeing cycle, the bath is drained to remove all dyeing aids, i.e. all the liquid remaining in the bath after completion of the dyeing process.

The bath containing the dyed fiber is then replenished with cold water in a weight ratio of 15-100:1 based on the weight of the wool. To this replenished bath is added a surfactant, preferably an anionic surfactant, in an amount effective as a synthetic tanning agent (syntan) and allowing the diffusion of a syntan into the peripheral region of the wool fiber, the weight ratio preferably being 0.5-1.5% based on the weight of the wool in the bath. A fluorochemical is added to the bath in an amount sufficient to interact with the stain-proofing agent to provide improved stain-proofing properties compared to a fabric treated in the same manner without the fluorochemical, the weight ratio preferably being 0.5-1.5% based on the weight of the fiber. A stain-resistant agent is added in an amount sufficient to reduce appreciably the adsorption of stain-forming material and thereby minimize the treatment required to protect the wool fiber, preferably in a weight ratio of 1.5 - 5%, based on the weight of the fiber. If necessary, an acid, preferably a strong acid, is also added to the same bath, sufficient to lower the pH of the bath to 1.5 - 3.0.

After the refilled bath mixture is complete, the refilled bath containing the fabric is maintained for a time and at a temperature sufficient to allow absorption of the bath components by the fabric in an amount effective to impart stain-resistant properties to the material. For example, the temperature of the refilled bath may be increased to 45 - 75ºC and the temperature maintained at that level for 15 - 60 minutes. The preferred bath temperature is 60 - 65ºC and the preferred residence time is 20 minutes.

After this period, all unabsorbed liquid is discharged from the replenishment bath, with water being added to aid cooling and to ensure that the bath overflows to adequately discharge liquid. Without the addition of water, the fiber can become unacceptably compact and stiff.

In addition to the protective treatment specified above, a further tip sealing process may be carried out if desired. This tip sealing process is used when the bulked wool is applied to a backing to make a carpet. The tip sealing compound, which is preferably in The top-sealing process, which is in the form of a polymethacrylic resin combined with a fluorochemical mixed with a surfactant, can be applied by either spraying or foaming. This top-sealing process adds an additional layer of protection to the surface of the carpet, whose wool fibers are normally sheared to the same height along the length of the carpet. The top-sealing process provides additional protection against acid dyes, footprints (from dirt, etc.) and especially coffee stains. The polymethacrylic type resin and the fluorochemical mixed with a surfactant are mixed and added to the carpet surface in a weight ratio of 0.25-1.0% resin and 0.25-1% fluorochemical mixed with a surfactant, based on the weight of the wool fiber.

Regarding the protection system fundamental to this invention, it is noted that the fluorochemical used in this process imparts certain lubricious properties to the fiber to which the system is applied. During the blending of the wool fiber base, a suitable spinning lubricant useful in spinning the wool is conventionally added. The use of the above fluorochemical in the system of the present invention allows the amount of this spinning lubricant used to be reduced to between 40 and 60% of the concentration normally used thereof.

As an alternative to the refill bath process, a leaching process can be used. In this "leaching" process, the bath is not drained after the dyeing cycle has been completed, but the leaching (i.e. the bath liquid remaining after dyeing has been carried out) is cooled to a temperature and held at that temperature for a specific period of time, under conditions suitable to impart stain-resistant properties to the material. The leaching has a temperature of 65-75ºC, preferably 68-70ºC, and is held at that temperature for 10 to 40 minutes, preferably 30 minutes, and the stain-resistant agent is added. Acid is then added to adjust the pH of the resulting bath to a value of 2.0 to 2.5. The fluorochemical can be added either after the colorant or before the addition of the stain-resistant agent. The preferred amount of fluorochemical is 0.3 - 1.0% by weight of the fiber.

This alternative method saves processing time since the bath is not emptied (drained) after dyeing has been carried out and the bath temperature does not have to be increased from the ambient temperature as in the case of the refilled bath.

As shown above, the method of the present invention can be applied at any suitable stage of the manufacturing process, preferably at the Fiber base material before cutting the fiber base material or on the fiber strand before forming into a cone spool.

The process of the present invention can be applied to keratinous or other fibers after bulking. In such a case, it is preferred to use an embodiment of the present invention which provides a continuous rather than a two-stage process. In this embodiment, the bulked, undyed fiber is fed to a pre-wetting station and a surfactant, preferably anionic, is added in a weight ratio of 0.5 to 4% surfactant based on the weight percent moisture uptake of the fiber, which is in the range of 80 to 100%. A mordant, preferably a trivalent mordant, is added in a weight ratio of 0.5 to 2% based on the weight percent moisture uptake of the fiber. Thereafter, an anionic surfactant in an amount of 0.5 to 4 wt.%, a divalent salt in an amount of 0.5 to 2 wt.%, an inorganic fluorochemical in an amount of 0.5 to 2 wt.%, a stain-resistant agent in an amount of 1.5 to 5 wt.% and, if necessary, an acid to lower the pH of the solution to 1.5 to 3, based on 200 to 600% percent moisture content of the fiber with a Brookfield viscosity of 40 to 60 cPoise, are added to the flow dyeing device, overflow applicator or pad dyeing mangle.

The carpet treated in this way is treated with saturated steam for 3 to 10 minutes, followed by normal rinsing and extraction until the fibers have absorbed 80 - 100% of the moisture.

When dyeing the bulked fiber is desired in the process of this embodiment of the present invention, the dye is added simultaneously with the fluorochemical and the stain resist.

In any embodiment of the system of the present invention, the following chemical substances are preferred:

The mordant may be any trivalent or tetravalent mordant suitable for use with the fiber to which the process of the present invention is applied.

Likewise, the surfactant may be anionic, cationic, nonionic, amphoteric or other surfactant suitable for use with the fiber. Anionic surfactants are preferred. Suitable anionic surfactants include:

alkylarylsulfonated and hydroxyethylated fatty acid amines and their derivatives, such as Univadin PS-AU (Ciba-Geigy); sodium alkyldiphenyl ether disulfonates, such as Pelex SS-L (Kao Corporation); sodium dodecyldiphenyl oxide disulfonate with strong sulfur bond (ammonium thiosulfate containing), such as Pelex SS-H; the disodium salt of dodecyl(sulfophenoxy)benzenesulfonic acid; the disodium salt of oxybis(dodecylbenzenesulfonic acid), such as Rhodacal DSB, Siponat DSB (Rhone Poulenc); a solution of hydrotropic sodium xylenesulfonate, Kemmat SN18 (Harcros Chemicals); arylsulfonates, fatty acid amine polyglycol ether (sulfonate ethylene oxide condensate), such as TEBAN ES (Dr. Th. Böhme Chemie); the sodium salt of a heavily sulfonated oil/ethylene oxide condensate, such as MATEXIL LA-NS (ICI); the disodium salt of dodecyl(sulfophenoxy)benzenesulfonic acid, the disodium salt of oxy-bis(dodecylbenzenesulfonic acid) containing at least 1% sodium sulfate and at least 3% sodium chloride, such as Dowfax 2-Al (Dow Chemicals); general groups of alkylated diphenyl oxide disulfonates used as dispersants of the formula:

sulfated monoesters of a fatty acid containing a sodium salt such as LANKROPOL WN (Lankro Chemicals) or an ammonium salt such as LANKROPOL WA (Lankro Chemicals) or a potassium salt such as LANKROPOL OPA (Lankro Chemicals); and the disodium and monosodium salt of dodecyl(sulfophenoxy)benzenesulfonic acid and of didodecyldisulfonated diphenyl oxide such as CALFAX DB-45 (Pilot Chemicals)

The fluorochemical compositions useful in the present invention include anionic, cationic, or nonionic fluorochemicals such as the fluorochemical miophanates disclosed in U.S. Patent No. 4,606,737 (Stern); the fluorochemical polyacrylates disclosed in U.S. Patent Nos. 3,574,791 (Sherman et al.) and 4,147,851 (Raynolds); the fluorochemical urethanes disclosed in U.S. Patent No. 3,398,182 (Guenther et al.); the fluorochemical caibodiimides disclosed in U.S. Patent No. 4,024,178 (Landucci) and the fluorochemical guanidines disclosed in U.S. Patent No. 4,540,497 (Chang et al.).

Preferred fluorochemicals include the fluorochemicals described in detail in the examples below.

The stain protection agent (or stain preventer) may be any chemical substance suitable for use with fiber materials, preferably keratinous fiber materials, and includes sulfonated phenolic resins and derivatives such as FX-369 (3M),

with at least 40 % SO₃X residues and 40 % -

Groups; preferably leather syntans,

containing naphthalene sulfones and derivatives thereof, such as PARALEN WXA (sodium salts of naphthalenesulfonic acid, formaldehyde and sulfonylbis(phenol)) (Yorkshire Chemicals),

a.

Other suitable stain protection agents can easily be selected by the specialist.

The preferred stain-blocking mixture, which includes the stain-blocking agent and the surfactant, consists of:

62 - 80%, preferably 72%, Paralen WXA,

13 - 25 %, preferably 18.2 %, Kemmat SN18 and

7 - 13%, preferably 9.8%, Siponat DSB.

The acid to be used in the process is, if necessary, preferably a strong acid, e.g. amidosulfuric acid, formic acid or sulfuric acid.

The spinning lubricant is used in an amount of 40 - 60% of the normal amount (i.e. 40 - 60% of 0.8 - 1.2% of the dry weight of the wool), preferably in an amount of 0.4 to 0.6% for the dry spinning process. A lubricant with a low soil attraction behavior is selected. Suitable lubricants include Cirrasol ALN-W3 (alkoxylated glycerol and polyethylene glycol) (ICI Chemicals); or the high wetting version of Cirrasol ALN-W6 (ICI Chemicals);

Crosslube DBS (polyglycol and phosphate ester) (Crossfield Textile Chemicals); or Nopcostat 725-A (polyethoxylated cetyl oleyl alcohol). The moisture content preferably added to the wool base is in the range of 14 - 17%, most preferably 14 - 15%.

The tip seal compound preferably contains alpha-olefin sulfonate and 0.25% - 1.0% owg (weight or percentage based on the weight of the fiber, which is 100%) of a polymethacrylate polymer, such as a blend comprising (a) about 23 parts of a copolymer of methacrylic acid (described in U.S. Patent No. 4,937,123 (Chang et al.) as Polymer H, using butyl acrylate instead of ethyl acrylate and the weight ratios are about 78.4 parts methacrylic acid, about 17.6 parts butyl acrylate, about 2 parts sulfonated castor oil, and about 2 parts NaOH); (b) about 3.4 parts of a partially sulfonated novolak resin (FC-369, available from 3M); (c) about 8 parts Witconat AOS at 39% solids and about 64 parts water, and (d) 0.25% - 1.0% owg of a sorbitan mono-9-octadecenoate-containing fluoroaliphatic polymer such as a mixture described in Example 8 of U.S. Patent No. 4,264,484 (Patel) comprising (i) a fluoroaliphatic ester containing radicals and chlorine atoms and (ii) a water-insoluble addition polymer, the ratio of ester to addition polymer being about 1.7:2 instead of 1:2, and to which is added about 7.1% (based on ester and addition polymer solids) Witconat AOS solid.

An authentic fluorochemical together with the stain repellent provides optimal oil, water and soil repellency in conjunction with the stain repellent properties (particularly desorption of acidic dye) of the stain repellent.

Temperature: The diffusion rate of the stain repellent is most effective in the range of 45 - 80ºC without causing a change in the shade of the fiber or yarn, and the ideal condition for the absorption of the applied fluorochemical by the fibers is at temperatures above 60ºC. This temperature range allows for slow but effective and uniform absorption.

pH conditions: While a high temperature creates a preferential medium for the absorption of the chemicals, a low pH facilitates their fixation to wool fibers through ionic, hydrogen and covalent bonding. A pH range of 2.0-2.5 minimizes the yellowing effect often associated with sulfonated compounds.

The top sealing process is particularly useful for increasing the overall performance of the stain protection properties on wool carpets, especially for carpets with a sheared pile. A novel feature is the use of polymethacrylate resin without rinsing, without fear of yellowing. This, in combination with a fluoroaliphatic polymer containing a surfactant, facilitates penetration through Migration. It is essential that the compound can be applied by spraying or foaming as described.

Test results

Tests on wool carpet samples treated with the method of the present invention will now be described by way of example only.

1. Stain protection test

The following stain test is used in the examples: IWS test method No. 282/1991 "Test method for evaluating the tendency to stain of textile floor coverings". This test evaluates the tendency of samples of finished wool carpet samples to stain in "new" and "used" conditions, i.e. before and after (simulated) walking using red FD&D food dye medium. The test was designed to evaluate the effect and durability of the stain-resistant finish on wool carpets. A 24-hour stain protection rating of the unused samples of #6 is satisfactory; a rating of #7 is considered good, and a rating of #8 is excellent.

A 24-hour stain protection rating of #3 is satisfactory for used samples; #5 is good and #7 is excellent.

2. Stain repellency test

In the example, the following test is used: IWS test method no. 258/1985 "Test method for evaluating the oil and water repellency of textile floor coverings". This test evaluates the oil and water repellency properties of textile floor coverings that have been treated with an anti-stain or anti-dirt finish.

Minimum ratings of #4 for oil (n-tetradecane) and #3 for water (70/30 water/isopropanol) are considered satisfactory.

3. Accelerated contamination test

In the example, the following test is used: IWS test method no. 267/1991 "Test method for evaluating the soiling tendency of floor coverings". This test is intended to evaluate the soiling tendency of wool carpets using an artificial soil composition.

A minimum rating of #3 on the gray scale (ISO R105, Part 3) is considered satisfactory, a rating of #4 is good, #5 is excellent.

4. Colour fastness to light

In the examples, the following test is used: IWS test method No. 133/1985 "Colour fastness of textile floor coverings to light". This test is intended to evaluate the colour fastness of textile floor coverings made of wool and wool-rich mixtures to the effect of an artificial light source whose spectrum closely corresponds to that of daylight. The method is based on ISO 105-302: 1984 Colour fastness to light; Xenon arc lamp.

The following ratings are considered satisfactory:

Standard depth: Minimum 5

1/12 and less of standard depth: Minimum 4

First fading: Minimum 3

I. Example of continuous application

The example uses a bulked 100% pre-dyed New Zealand wool carpet sample (100g) weighing 1422 gsm.

Step 1 - Pre-wetting

Padding dyeing mangle pre-wetting station with a moisture absorption of up to 100%, where one litre of solution contains the following components:

- 0.5 g/l dioctylsulphosuccinic acid surfactant, such as Bevaloid 1299 (Rhone Poulenc).

- 0.5 % owg (5 g) trivalent mordant aluminium sulphate.

Step 2- Applying

Overflow application device that achieves 300% absorption of the following components:

- Guarana up to a Brookfield viscosity of 50 cPoise;

- 2% owg (6.7 g) alkylarylsulfonated and hydroxyethylated fatty acid amines as anionic leveling agents, such as Univadin PS-AU (Ciba-Geigy);

- 0.5% owg (1.7 g) divalent salt, such as magnesium chloride;

- 0.75% owg (2.5 g) of a mixture as described in Example 8 of U.S. Patent No. 4,264,484 (Patel) comprising (i) a fluoroaliphatic ester containing radicals and chlorine atoms and (ii) a water-insoluble addition polymer, wherein the ratio of ester to addition polymer is about 1.7:2 instead of 1:2, and to which is added about 7.1% by weight (based on ester and addition polymer solids) of Witconate AOS solid;

- 2% owg (6.7 g) naphthalenesulfonic acid Paralen WXA (Yorkshire Chemicals); with a

- pH value of 2.2, adjusted with amidosulfuric acid.

Step 3 - Fix

The coated sample was exposed to saturated steam for 10 minutes to fix it. After 10 minutes, the sample was cooled for 1 minute, then washed thoroughly and extracted to a moisture content of about 50% built-in moisture.

Step 4 - Tip sealing procedure

The dehydrated sample was oversprayed to 10% absorption with a top sealing chemical made from the following mixture:

- 0.5% owg of a mixture comprising (a) about 23 parts of a copolymer of methacrylic acid (described in U.S. Patent No. 4,937,123 (Chang et al.) as Polymer H, using butyl acrylate instead of ethyl acrylate and the weight ratios are about 78.4 parts methacrylic acid, about 17.6 parts butyl acrylate, about 2 parts sulfonated castor oil, and about 2 parts NaOH); (b) about 3.4 parts of a partially sulfonated novolak resin (FC-369, available from 3M); (c) about 8 parts Witconate AOS at 39% solids and about 64 parts water, and

- 0.5% oww of a mixture as described in Example 8 of U.S. Patent No. 4,264,484 (Patel) comprising (i) a fluoroaliphatic ester containing radicals and chlorine atoms and (ii) a water-insoluble addition polymer, wherein the ratio of ester to addition polymer is about 1.7:2 instead of 1:2, and to which is added about 7.1% by weight (based on ester and addition polymer solids) of Witconat AOS solid.

The sample was then dried and cured at 120ºC for 20 minutes. After conditioning to room temperature, the sample was subjected to the following tests, the results of which are given below:

Note: N/A means "not rated".

II. Example of application using the strand dyeing process Step 1 - Applying stain

In the example, an undyed 7 kg wool skein was placed in a skein dyeing machine. 0.5% owg (35%) mordant was added to the standard dye bath containing pre-metallized dyes. The dyeing process was carried out using the standard procedure in a vertical milling machine, heating the dye liquid to 98ºC over 50 minutes and holding it at this temperature for 20 minutes.

Step 2 - Absorption of protective chemicals

The bath was drained and refilled with cold water (140 l bath water = liquid ratio of 20:1).

The following chemicals were added to this bath:

- 2% owg (140 g) sodium alkyl diphenyl ether disulfonate, such as Pelex SS-L (Kao Corp.),

- 2% owg (140 g) naphthalenesulfonic acid, such as Paralen WXA (Yorkshire Chemicals),

- 0.75% owg (52.5 g) of a fluorochemical composition comprising a mixture of (a) a water-insoluble fluoroaliphatic radical-containing ester and chlorine atoms; (b) a water-insoluble fluoroaliphatic radical-containing polymer; and (c) a water-insoluble fluoroaliphatic radical-containing compound selected from carbonylimino compounds and imine compounds described in Example 14 of U.S. Patent No. 4,401,780 (Steel), except that component (a) contains about 69 wt.%, component (b) about 16 wt.% and component (c) about 15 wt.%.

The bath was circulated for 5 minutes and

- 1.6 g/l amidosulfuric acid (224 g) adjusted to a pH of 2.4.

The temperature was then raised to 65ºC over 40 minutes and held for 20 minutes. The bath was then drained, refilled with cold water, rinsed for 10 minutes, and then drained, leaving it dripping wet.

Step 3 - Tip sealing procedure

During the application of the carrier, the bulked sample with the requirements of the treated yarn was subjected to a surface tip seal spray treatment with 10% moisture cream, the mixture containing the following ingredients:

- 0.5% owg of a polymethacrylic polymer, a mixture comprising (a) about 23 parts of a copolymer of methacrylic acid (described in U.S. Patent No. 4,937,123 (Chang et al.) as Polymer H, using butyl acrylate instead of ethyl acrylate and the weight ratios are about 78.4 parts methacrylic acid, about 17.6 parts butyl acrylate, about 2 parts sulfonated castor oil, and about 2 parts NaOH); (b) about 3.4 parts of a partially sulfonated novolac resin (FC-369, available from 3M); (c) about 8 parts Witconate AOS at 39% solids and about 64 parts water, and

- 0.5% owg of an anionic fluorochemical emulsion as described in Example 8 of U.S. Patent No. 4,264,484 (Patel), a mixture comprising (a) a fluoroaliphatic ester containing radicals and chlorine atoms and (b) a water-insoluble addition polymer, the ratio of ester to addition polymer being about 1.7:2 instead of 1:2, to which is added about 7.1% by weight (based on ester and addition polymer solids) of Witconate AOS solid.

The sample was then dried and cured for the same period of time as a latex-coated jute backing in a carpet fulling machine.

After conditioning to room temperature, the sample was subjected to the following tests, the results of which are given below:

(For test procedures see Example I Continuous Application)

III. Example of application in the dyeing process in the flake Step 1 - Applying stain

In the example, 70 kg of wool fleece in the form of the loose fiber base material was placed in a commercially available vat for dyeing in the flake. The liquid ratio was 63:1.

0.5% owg (350 g) of aluminium sulphate was added to the side vat after the dyes and fed to the main vat. The dyeing process was carried out in the usual manner using a low temperature dyeing process. The bath was heated to 80ºC over 50 minutes and held at this temperature for 20 minutes.

The bath was then drained and the tub refilled with cold water

Step 2 - Absorption of protective chemicals

The refill bath had a liquid ratio of 63:1. The following chemicals were added:

- 2% owg (1.4 kg) sodium alkyl diphenyl ether disulfonate, such as Pelex SS-L (Kao Corp.),

- 2% owg (1.4 kg) naphthalenesulfonic acid, such as Paralen WXA (Yorkshire Chemicals),

- 0.75% owg (0.530 kg) of a fluorochemical composition comprising a mixture of (a) a water-insoluble, fluoroaliphatic, radical-containing ester and chlorine atoms; (b) a water-insoluble, fluoroaliphatic, radical-containing polymer; and (c) a water-insoluble, fluoroaliphatic, A radical-containing compound selected from the group consisting of carbonylimino compounds and imine compounds described in Example 14 of U.S. Patent No. 4,401,780 (Steel), except that component (a) was about 69 wt.%, component (b) was about 16 wt.%, and component (c) was about 15 wt.%.

The bath was circulated for 5 minutes and adjusted to a pH of 2.4 with - 1.6 g/l amidosulfuric acid (7 kg).

The temperature was then raised to 65ºC over 30 minutes and the bath was held at this temperature for 20 minutes. After this absorption process, the bath was drained and the fiber base was rinsed as in the conventional process.

Step 3 - Yarn processing

The fiber stock was then dried and cut. The dry spinning process was used using 0.5% spinning lubricant, Nopcostat 725-A. The remaining process was carried out until a bulked carpet was obtained.

Step 4 - Tip sealing procedure

During the application of the carrier, the bulked sample with the requirements of the treated fiber base was subjected to a surface top seal spray treatment with 10% moisture absorption, the mixture containing the following ingredients:

- 0.5% owg of a polymethacrylic polymer, a mixture comprising (a) about 23 parts of a copolymer of methacrylic acid (described in U.S. Patent No. 4,937,123 (Chang et al.) as Polymer H, using butyl acrylate instead of ethyl acrylate and the weight ratios are about 78.4 parts methacrylic acid, about 17.6 parts butyl acrylate, about 2 parts sulfonated castor oil, and about 2 parts NaOH); (b) about 3.4 parts of a partially sulfonated novolac resin (FC-369, available from 3M); (c) about 8 parts Witconate AOS at 39% solids and about 64 parts water, and

- 0.5% oww of an anionic fluorochemical emulsion as described in Example 8 of U.S. Patent No. 4,264,484 (Patel), a mixture comprising (a) a fluoroaliphatic ester containing radicals and chlorine atoms and (b) a water-insoluble addition polymer, the ratio of ester to addition polymer being about 1.7:2 instead of 1:2, to which is added about 7.1% by weight (based on ester and addition polymer solids) of Witconate AOS solid.

The sample was then dried and cured for the same period of time as a latex-coated jute backing in a carpet fulling machine.

After conditioning to room temperature, the sample was subjected to the following tests, the results of which are given below:

(For the test procedures see Part I)

IV. Example of application in the lye wool dyeing process in the flock

In the example, 1000 kg of wool in the form of the loose fiber base material was placed in a commercially available vat for dyeing in the flake. The liquid ratio was 10:1.

Step 1 Applying the fluorochemical

- Loading the main dyeing vat with 100 kg of wool base material and 10,000 l of water; Starting the circulation;

- Addition of leveling agent;

- addition of colorants;

- addition of acid;

- Addition of magnesium chloride in an amount of 0.5% by weight based on the weight of the wool (5 kg).

- Addition of the fluorochemical in an amount of 0.5% by weight based on the weight of the wool (5 kg). The fluorochemical was a mixture of (a) a water-insoluble fluoroaliphatic radical-containing ester and chlorine atoms; (b) a water-insoluble fluoroaliphatic radical-containing polymer; and (c) a water-insoluble fluoroaliphatic radical-containing compound selected from carbonylimino compounds and imine compounds, described in Example 14 of U.S. Patent No. 4,401,780 (Steel), except that component (a) was about 69 wt.%, component (b) was about 16 wt.%, and component (c) was about 15 wt.%.

The dyeing process was carried out in the usual way at the boiling point (98ºC). After completion of the dyeing cycle, the spent liquor was cooled to 70ºC as in the normal process.

Step 2 - Applying the stain repellent

- The mixture of stain repellent and surfactant was added in diluted form to the vat in an amount of 4.5% by weight based on the weight of wool (45 kg);

- sulphuric acid was then added to adjust the pH to pH 2.4 ;

- the bath was held for 30 minutes, then drained, and the fibre base was rinsed for 10 minutes before draining.

Step 3 - Yarn processing

- The fiber base was dried and mixed with 0.5% spinning lubricant, Nopcostat 725-A; the moisture content was adjusted to 16% in the mixing stage to obtain 14% in the storage room.

- The fibre base was carded and spun successfully without any special measures.

- The yarn was twisted into two layers, wound into a skein and autoclaved as in the normal procedure.

Step 4 - Tip sealing procedure

During the application of the carrier, the bulked sample with the requirements of the treated fiber base was subjected to a surface top seal spray treatment with 10% moisture pick-up, the mixture containing the following ingredients:

- 0.5% owg of a polymethacrylic polymer, a mixture comprising (a) about 23 parts of a copolymer of methacrylic acid (described in U.S. Patent No. 4,937,123 (Chang et al.) as Polymer H, using butyl acrylate instead of ethyl acrylate and the weight ratios being about 78.4 parts methacrylic acid, about 17.6 parts butyl acrylate, about 2 parts sulfonated castor oil and about 2 parts NaOH); (b) about 3.4 parts of a partially sulfonated Novolak resin (FC-369, available from 3M); (c) about 8 parts Witconat AOS at 39% solids and about 64 parts water, and

- 0.5% owg of an anionic fluorochemical emulsion as described in Example 8 of U.S. Patent No. 4,264,484 (Patel), a mixture comprising (a) a fluoroaliphatic ester containing radicals and chlorine atoms and (b) a water-insoluble addition polymer, the ratio of ester to addition polymer being about 1.7:2 instead of 1:2, to which is added about 7.1% by weight (based on ester and addition polymer solids) of Witconate AOS solid.

The sample was then dried and cured for the same period of time as a latex-coated jute backing in a carpet drying machine.

After conditioning to room temperature, the sample was subjected to the following tests, the results of which are given below:

(For test procedures see Example I Continuous Application)

Claims (20)

1. A process for imparting stain resistance to acid dyes to synthetic or keratinous fibre material, the process comprising the steps of: A. Treating the material with a trivalent or tetravalent mordant in an amount effective to impart improved stain resistance to the fibre; B. Treating the material of step A. in an aqueous bath containing a surfactant selected from sulfonated and disulfonated surfactants in an amount effective to permit diffusion of a stain-resistant chemical into the fiber material and a stain-resistant chemical in an amount sufficient to appreciably reduce adsorption of stain-forming material by the fiber, the pH of the bath being from 1.5 to 3.0, and a fluorochemical is present in either step A. or B. in an amount sufficient to impart improved stain resistance properties to the fibrous material. 2. The method according to claim 1, wherein (i) the fibre material is wool; (ii) the mordant is selected from aluminium sulphate, aluminium hydroxide or a zirconium salt, selected from zirconium sulphate or zirconium hydroxide; and (iii) the amount of mordant used is between 0,5 and 2 % by weight based on the weight of the wool, which is 100 %. 3. A method according to claim 1, wherein the fiber material is wool and to which the following conditions apply: i) Step A. is carried out in a dye bath in the presence of a dye at 80ºC to 98ºC; (ii) the dyebath is emptied after completion of the dyeing process and before step B. iii) in the aqueous bath of step B: a) the weight ratio of water to wool is in the range of 15 to 100:1; (b) the surfactant comprises an anionic surfactant mixture of sodium xylene sulphonate or derivatives thereof and dodecylbenzene sulphonic acid or derivatives thereof, and the weight ratio of surfactant to wool is 0.5 - 1.5% based on the weight of wool, which is 100%; (c) the weight ratio of fluorochemical to wool is 0.5 - 1.5%, based on the weight of wool, which is 100%; (d) the stain-resistant chemical comprises naphthalene sulphonic acid or a derivative thereof and the weight ratio of stain-resistant chemical to wool is 0.5 - 5% based on the weight of wool, which is 100%; and (e) the weight ratio of stain-resisting chemical to surfactant is in the range 62/38 to 80/20 and within the 38-20 surfactant ratio, the sodium xylene sulphonate type surfactant accounts for about 13-25 parts and the surfactant Substance of the dodecylbenzenesulfonic acid type makes up about 7 - 13 parts. 4. The process of claim 3, wherein the temperature of the aqueous bath of step B. is 45°C to 80°C and it is maintained at that temperature for 15 to 60 minutes. 5. The method of claim 1, wherein: (i) step A. is carried out in a dye bath in the presence of a dye and the bath from step A. remaining after the dyeing process is a waste liquor, the temperature of which is adjusted to a temperature at which stain resistance properties can be imparted to the fibre material; and (ii) the stain resisting chemical and the surfactant are added to the spent liquor as part of step B and the surfactant is added in an amount sufficient to reduce the amount of stain resisting chemical. 6. The method of claim 5, wherein: i) the temperature in step B is 65ºC to 75ºC and the treatment time in step B is 10 - 40 minutes ; and (ii) the ratios of stain resistance chemical to surfactant, expressed as percentages based on the weight of the fibre material, which is 100 %, are 1,5-5,0 % and 0,5-1,5 %. 7. The method of claim 6, wherein the pH of the bath of step B. is 2.0 - 2.5. 8. The method of claim 7, wherein the fluorochemical is used in a proportion of 0.3 - 1.0% based on the weight of the fiber material, which is 100%, and the fluorochemical is added either immediately after the addition of the dye in step A. or immediately before the addition of the stain-resistant chemical in step B. 9. A method according to claim 8, wherein the stain-resistant chemical comprises naphthalenesulfonic acid or a derivative thereof and the surfactant is a mixture of sodium xylenesulfonate or derivatives thereof and dodecylbenzenesulfonic acid or derivatives thereof. 10. The method of claim 9 wherein the weight ratio of stain resisting chemical to surfactant is in the range of 62/38 to 80/20 and within the 38-20 ratio of surfactant, the sodium xylene sulfonate type surfactant is about 13-25 parts and the dodecylbenzene sulfonic acid type surfactant is about 7-13 parts. 11. The method of claim 1 wherein the fibrous material is keratinous, the material is fluffed and a carrier material is applied to the underside of the fluffed material, and after fluffing and applying the carrier material, the further step of tip sealing is performed, wherein tip sealing comprises applying to the fluffed material a solution comprising a polymethacrylic resin and a fluorochemical mixed with a surfactant. 12. The process of claim 1, wherein the surfactant is anionic and is selected from alkylarylsulfonated fatty acid amines, hydroxyethylated fatty acid amines, sodium alkyl diphenyl ether disulfonate, sodium dodecyl diphenyl oxide disulfonate, the disodium salt of dodecyl (sulfophenoxy) benzene sulfonic acid, the disodium salt of oxybis (dodecylbenzene sulfonic acid), hydrotropic sodium xylene sulfonate, aryl sulfonates, fatty acid amine polyglycol ether (sulfonate ethylene oxide condensate), the sodium salt of a strongly sulfonated oil/ethylene oxide condensate, the disodium salt of oxy-bis (dodecylbenzene sulfonic acid) containing at least 1% sodium sulfate and at least 3% sodium chloride, groups of alkylated diphenyl oxide disulfonates of the formula: sulfated monoesters of a fatty acid containing a sodium, ammonium or potassium salt, the disodium and monosodium salt of dodecyl(sulfophenoxy)benzenesulfonic acid containing didodecyldisulfonated diphenyl oxide. 13. The method of claim 1, wherein the fluorochemical is selected from fluorochemical allophants, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides and fluorochemical guanidines. 14. The method of claim 1, wherein the stain-resistant chemical is selected from sulfonated phenolic resins, naphthalene sulfones and derivatives thereof. 15. A method of imparting stain resistance to acid dyes to keratinous fiber material, the method comprising the steps of: A. Preparation of the keratinous fiber material in puffed form, B. Transporting the bulked keratinous fiber material through a pre-wetting system and adding a first surfactant, C. adding a trivalent or tetravalent mordant to the pre-wetted keratinous material of step B. in an amount sufficient to impart improved stain resistance to the fiber, and D. Contacting the keratinous material with an aqueous mixture of a second surfactant together with a divalent salt, an anionic fluorochemical and a stain resisting chemical in an amount sufficient to significantly reduce the adsorption of staining material by the fiber, the mixture having a pH of 1.5-3.0. 16. The method of claim 15, wherein the keratinous material is wool, and: i) the first surfactant is anionic, comprising a mixture of sodium xylene sulphonate or derivatives thereof and dodecylbenzene sulphonic acid or derivatives thereof and is added to the bulked wool in a weight ratio of 0.5 - 4% based on the weight of the wool, which is 100%, (ii) the stain-resistant chemical substance comprises naphthalenesulfonic acid or derivatives thereof, and (iii) the weight ratio of stain resistance chemical to surfactant Substance is in the range of 62/38 to 80/20 and within the 38 - 20 surfactant proportion, the sodium xylene sulfonate-TVP surfactant accounts for about 13 to 25 parts and the dodecylbenzene sulfonic acid type surfactant accounts for about 7 to 13 parts. 17. The method according to claim 16, wherein the mordant i) is selected from aluminium sulphate, aluminium hydroxide or a zirconium salt selected from zirconium sulphate or zirconium hydroxide, and (ii) is present in a proportion of 0.5 to 2 % by weight, based on the weight of the wool, which is 100 %. 18. The method according to claim 15, wherein the weight proportions of the different components, based on the weight of the keratinous material, which is 100%, have the following values: i) second surfactant: 0.5 - 4.0 %, ii) divalent salt: 0.5 - 2.0 %, iii) anionic fluorochemical: 0.5 - 2.0% and iv) Chemical imparting stain resistance: 1.6 - 5.0%. 19. The method of claim 15, wherein the second surfactant is selected from alkylarylsulfonated fatty acid amines, hydroxyethylated fatty acid amines, sodium alkyldiphenyl ether disulfonate, sodium dodecyldiphenyl oxide disulfonate, the disodium salt of dodecyl(sulfophenoxy)benzenesulfonic acid, the disodium salt of oxy-bis(dodecylbenzenesulfonic acid), hydrotropic sodium xylenesulfonate, arylsulfonates, fatty acid amine polyglycol ether (sulfonate ethylene oxide condensate), the sodium salt of a highly sulfonated oil/ethylene oxide condensate, the disodium salt of oxy-bis(dodecylbenzenesulfonic acid) containing at least 1% sodium sulfate and at least 3% sodium chloride, groups of alkylated diphenyl oxide disulfoates of the formula: sulfated monoesters of a fatty acid containing a sodium, ammonium or potassium salt, the disodium and monosodium salt of dodecyl(sulfophenoxy)benzenesulfonic acid containing didodecyldisulfonated diphenyl oxide. 20. The method of claim 15, wherein the stain-resistant chemical is selected from sulfonated phenolic resins, naphthalene sulfones and derivatives thereof.