EP0467246A1 - Process of antisoiling finishing of textile material of polyamide or wool - Google Patents

Abstract

Process for soil resist finishing of textile material in wool or polyamide by treating the textile material with a condensation product of a bicyclic phenol of the formula 1 <IMAGE> where X is a direct bond or a bridge member of the formula -SO2-, -SO-, -S-, -CH2-, -C(CH3)2- or -CO-, preferably -SO2-, n and n' are each 1 or 2, m and m' are each 0, 1 or 2, and Me is hydrogen or an alkali or alkaline earth metal or ammonium ion, with formaldehyde and amidosulphuric acid, or alkali or alkaline earth metal or ammonium salts thereof.

Description

The main component of modern carpet finishes contains so-called fluorocarbon resins, which give the material water and oil-repellent properties. Such formulations additionally contain a dirt-repellent component (stain blocker). Various condensation products of formaldehyde and sulfonated aromatic hydroxy compounds are known for this purpose (EP 242 496, EP 328 822, EP 332 343, US 4,839,212, US 4,822,373). All these products have in common that a sulfonic acid group is bonded directly to the aromatic ring.

wobei X eine direkte Bindung oder ein Brückenglied der Formel -S0₂-, -SO-, -S-, -CH₂-, -C(CH₃)₂- oder -CO-, vorzugsweise -S0₂-,

• n und n' die Zahlen 1 oder 2, m und m' die Zahlen 0, 1 oder 2 und Me Wasserstoff oder ein Alkali-, Erdalkali- oder Ammonium-lon bedeuten, mit Formaldehyd und Amidoschwefelsäure oder deren Alkali-, Erdalkali- oder Ammoniumsalze behandelt.

The invention relates to a process for the dirt-repellent finishing of textile material made of polyamide or wool, wherein the textile material with a condensation product of a dinuclear phenol of formula 1

where X is a direct bond or a bridge member of the formula -S0 ₂ -, -SO-, -S-, -CH ₂ -, -C (CH ₃ ) ₂ - or -CO-, preferably -S0 ₂ -,

• n and n 'are the numbers 1 or 2, m and m' are the numbers 0, 1 or 2 and Me is hydrogen or an alkali metal, alkaline earth metal or ammonium ion, with formaldehyde and amidosulfuric acid or their alkali metal, alkaline earth metal or ammonium salts treated.

In contrast to the stain blockers known from the prior art, not only sulfonic acid groups are present in the condensation products to be used according to the invention, but also groups of the formula -CH ₂ NHS0 ₃ Me. These condensation products and their preparation are known from DE-A 25 49 533. This document describes the suitability of these condensation products as an aid for improving the wet fastness of polyamide dyeings. An effect as a stain blocker is not mentioned there.

Binuclear phenols of the formula 1 are dihydroxydiphenyl sulfone, dihydroxydiphenyl sulfoxide, dihydroxydiphenyl sulfide, dihydroxydiphenylmethane, dihydroxydiphenyldimethylmethane, dihydroxybenzophenone and dihydroxydiphenyl, where the hydroxyl groups can be in the 4,4'-, 2,2'- or 4,2'-position 4,2 ', 4'-tetrahydroxydiphenyl sulfone, diphenyl sulfoxide, diphenyl sulfide, diphenyl methane, diphenyl dimethyl methane, benzophenone and diphenyl, and the derivatives derived therefrom by substitution with sulfonic acid groups. Those dinuclear phenols of the formula 1 in which X is a bridge member of the formula S0 ₂ are particularly advantageous. Furthermore, such dinuclear phenols of the formula 1 are preferably used for the preparation of the condensation products which contain at least one sulfo group.

Crude reaction products of phenol derivatives, in particular of phenol itself with sulfuric acid, oleum or sulfur trioxide, which can be obtained, for example, according to Ullmann, vol. 13, page 452, are also very suitable for producing the condensation products to be used according to the invention. These products can be used instead of the dinuclear phenol of formula 1 without isolation.

The formaldehyde used to prepare the condensates according to the invention can be used in the form of its aqueous solution, preferably a 30 to 39% by weight solution. Instead of formaldehyde, however, equivalent amounts of substances which release formaldehyde under the reaction conditions, such as e.g. Paraformaldehyde, urotropin or trioxymethylene.

To produce the condensation products to be used according to the invention, amounts of dinuclear phenol and formaldehyde are used such that the molar ratio of dinuclear phenol to formaldehyde is between 1.0: 0.7 and 1.0: 2.5. Sodium, potassium, calcium or ammonium sulfamate are preferred as sulfamates. These sulfamates or the amidosulfuric acid are used in an amount such that the molar ratio of dinuclear phenol to these modifiers is between 1.0: 0.1 and 1.0: 1.5.

The resins modified in this way additionally contain the group -CH ₂ -NH-S0 ₃ Me on the cores of the biphasic phenol of the formula 1, which is formed by reaction of methylol groups in the resin with the modifiers.

The condensation is carried out in such a way that mixtures of the dinuclear phenol of the formula 1 with formaldehyde or a substance which releases formaldehyde, a modifier, Water and, if the setting of a certain pH value is desired, an acid or base, with stirring to temperatures of about 60 to 1400 C, preferably 90 to 110 ° C are heated. The pH of the reaction mixture should preferably be between 7 and 11 during the condensation time. In a modification of this process, a mixture of dinuclear phenol and formaldehyde can also be precondensed and then reacted again with formaldehyde and sulfamate or amidosulfuric acid in a second step of this precondensate. The required condensation times depend on the desired degree of condensation. The degree of condensation largely determines the effectiveness of the condensation products. After a short condensation period, largely water-soluble condensation products are obtained. A degree of condensation should preferably be maintained, in which the condensation products have a K value of 7 to 17 in 5% aqueous solution.

The aqueous solutions thus obtained can be used directly as stain blockers. However, these aqueous solutions can also be converted into powder form beforehand by drying and then these powders can be dissolved again in water. The condensation products described can be applied to colored or uncolored substrates containing amino groups, such as wool or polyamide, or mixtures thereof with other fibers. They can be applied to these substrates alone or together with other water, oil and / or dirt-repellent products which contain perfluoroalkyl groups, insofar as the ionicity permits this. The condensation products can be used in the exhaust, padding or spraying process. It can also be used in the dye bath.

The necessary amounts to achieve a protective effect of the substrate are between 0.2% and 5%, usually between 1% and 2.5% of the active substance, based on the goods to be treated.

The condensation products are usually used at pH values between 2 and 5. If a pH value of 2 is chosen, the amount of product used can be reduced. The affinity (to the textile material) can also be increased by adding magnesium sulfate. The products pull at low temperatures such as well at room temperature. However, a more effective protective effect is achieved by increasing the bath temperature to 60 C to 80 C. In the pull-out process (with 0.8% based on the weight of the goods), an excellent protective effect is achieved at a pH of 2 and a temperature of 70 ° C.

In the case of a foulard application, a steaming process must be carried out before the goods receive a perfluorover spray and then dried and / or condensed. An effective protective effect is achieved with 1% of the goods at a pH of 2.

In the method described here, it is possible in comparison to conventional methods to work with smaller amounts of stain blockers with the same blocking effect. The high efficiency in use with a high protective effect and low tendency to yellowing is a significant advantage of the invention.

Use of stain blockers in the pull-out process (Linitest method)

In the pull-out process, the stain blockers are applied in an automatically working Linitest dyeing unit to strands of polyamide carpet yarn - freed from troublesome preparation residues. One strand is placed in a screwable stainless steel cylinder together with the equipment fleet. Up to twelve cylinders are held by a frame that is rotated in a water bath, the temperature, heating rate, dyeing time and cooling can be controlled automatically.

In a typical finishing bath, stain blockers are used at a liquor ratio of 1:20, the amount of which is 1% or 2.5%, based on the fiber weight. The stain blockers are applied at a pH of 2.5, which is adjusted by adding amidosulfuric acid. To improve the affinity, based on the fiber weight, 2% magnesium sulfate can be added.

After the solutions have been prepared, the cylinders are loaded with the appropriate equipment fleets. The polyamide strands to be treated, which had previously been slightly wetted with demineralized water, are then added to the cylinders so that they are well covered by the solutions.

The cylinders are placed in the dyeing unit at 30 C and left there for five minutes for conditioning. The water bath is now brought to the temperature required for the application of the stain blocker at two degrees per minute. The goods are usually treated at 70 ⁰ C ± 2 ° C to ensure that the products are pulled open. When this temperature is reached, the batches are allowed to act on the goods for 20 minutes before cooling to 30 ° C.

The treated goods are removed from the cylinders and rinsed well with cold, demineralized water. The strands are washed in succession with fresh water at a liquor ratio of 1:40 rinsed at room temperature and pressed by hand. The washed goods are centrifuged or squeezed on the padder to remove excess liquid. The mixture is then dried in a forced-air drying cabinet at 90 ° C. for 20 minutes.

The dry samples can then be tested using the test methods for soiling described below.

Soiling test

This test is used to quickly determine the stain blocker effectiveness against the staining of carpets by lemonade drinks, the acid dyes, e.g. C.I. Acid Red 40 included. The drinks used for the test, which can also contain sugar, citric acid, flavorings, vitamins and minerals, are commercially available products in the form of powder, which is dissolved in demineralized water according to the manufacturer's instructions. The dyeing liquors required for soiling the finished goods are created with the powder-containing powder dissolved in this way. They contain 90 g per liter of powder at a pH of about 3.

The soiling test is carried out in an automatically operating Linitest staining unit with up to 12 screwable stainless steel cylinders. The cylinders are each equipped with a test sample and the coloring soiling liquor.

SNIA carpet yarn 357 made of polyamide 6 is used as the test sample. It is trilobal 12 gauge yarn, fixed and without prior fluorine treatment. To remove preparation residues, the samples bound into strands (5 g ± 0.5 g) are boiled at a liquor ratio of 1:40 for 20 minutes in the presence of an oleyl sarcoside (1 g / l ^(R) Arkomon A conc.).

Then it is rinsed with deionized water for about five minutes without foam, the goods are freed from excess liquid by centrifuging or squeezing and dried at 90 ° C. in a forced-air drying cabinet for about 20 minutes.

Before the tests are carried out, the goods are well wetted with water and excess water is removed by centrifugation. Each stainless steel cylinder is loaded with a still wet test sample and filled with the soiling dye liquor so that the goods can be treated at a liquor ratio of 1:20 at 20 ° C ± 2 ° C for 30 minutes. The cylinders are held by a frame that is rotated in a water bath to guarantee the constant movement of the fleet.

The soiled samples are then rinsed under running cold, demineralized water until the rinsing water is no longer colored. The rinsed goods are centrifuged or squeezed to remove excess liquid and then linger for 20 minutes at 90 ° C. around a circulating air drying cabinet.

At the earliest one hour after drying, the samples soiled by dye are visually sampled against a standard. The depth of staining is assessed.

UV yellowing test (Xenotest)

The tendency to yellowing of goods equipped with stain blockers is determined by irradiating them with UV light for 16 hours. Equipped samples of 12 cm x 4 cm or tightly wound yarns with a winding width of 1 cm are twisted in the Xenotest 150 S at 30 C and 60% rel. Irradiated air humidity. They are then visually assessed against a running standard.

The following examples are intended to explain the process:

Examples

• 1. Under N ₂ are presented in the following order
  • 125.2 g (0.5 mol) 4,4'-dihydroxydiphenyl sulfone
  • 275 g of demineralized water
  • 60.5 g (0.5 mol) 33% NaOH
  • 25 g (0.25 mol) 30% formaldehyde solution
  
  and heated to 100 ° C for 2 hours. After cooling to room temperature, 193.7 g (0.65 mol) of 40% sodium sulfamate solution are added to this red-brown, clear solution, heated to 100 ° C. and 65.1 g (0.65 mol) of 30% formaldehyde solution are added dropwise over the course of 3 hours, and a further 6 Hold for hours at this temperature. 736.4 g of a brown, clear product are obtained; PH value: 9.0; Solids content: 31.3%; K value: 8.9.
• 2. In 500 ml stirred autoclaves are introduced one after the other under N ₂
  • 125.2 g (0.5 mol) 4,4'-dihydroxydiphenyl sulfone
  • 275 g of demineralized water
  • 63.1 g (0.65 mol) of amidosulfuric acid
  • 139.4 g (1.15 mol) 33% NaOH
  • 90.1 g (0.9 mol) 30% formaldehyde solution
  
  and heated for 1.5 hours at 130-135 C and 3-6 bar. A red-brown, clear liquid is obtained. pH: 9.0; Solids content: 34.6%; K value: 11.4.
• 3. In 500 ml stirred autoclave are placed under N ₂
  • 75.1 g (0.3 mol) of 4,4'-dihydroxydiphenyl sulfone
  • 165 g of demineralized water
  • 37.8 g (0.39 mol) of amidosulfuric acid
  • 83.6 g (0.69 mol) 33% NaOH
  • 54.1 g (0.54 mol) 30% formaldehyde solution
  
  and heated for 1 hour at 130-135 C and 4 bar. 404 g of a red-brown, clear liquid are obtained. pH: 9.0; Solids content: 36.8%; K value: 7.9.
• 4. Composition as Example 3. with a reaction time of 10 hours at 110 ° C at 3 bar. 152 g of deionized water are added. pH: 8.8; Solids content: 23.8%;
  • D ₂₀ = 1.12; K value: 10.4; Iodine color number: 40-60.
• 5. Composition as Example 3. with a reaction time of 30 hours at 90 C at 5 bar. pH: 9.1;
  • Solids content: 36.6%; D ₂₀ = 1.20; K value: 13.1;
  • Iodine color number: 90.
• 6. In 500 ml stirred autoclave are placed under N ₂
  • 125.2 g (0.5 mol) 4,4'-dihydroxydiphenyl sulfone
  • 233 g of demineralized water
  • 60.5 g (0.5 mol) 33% NaOH
  • 55 g (0.55 mol) 30% formaldehyde solution
  • and heated at 110 ° C for 2 hours. After cooling to room temperature
  • 193.7 g (0.65 mol) of 40% sodium sulfamate solution were added dropwise and the mixture was heated to reflux. Within 3.5 hours at this temperature
  • 65.1 g (0.65 mol) of 30% formaldehyde solution were added dropwise and the mixture was heated under reflux for a further 3.5 hours. 714 g of a red-brown, clear liquid are obtained. pH: 9.2; Solids content: 33.9%; K value: 11.5.
• 7. The 500 ml stirred autoclave are introduced one after the other under nitrogen
  • 100.1 g (0.5 mol) of 4,4'-dihydroxydiphenylmethane
  • 270 g of demineralized water
  • 58.3 g (0.6 mol) of amidosulfuric acid
  • 133.3 g (1.1 mol) 33% NaOH
  • 90.1 g (0.9 mol) 30% formaldehyde solution
  • and heated at 90 ° C for 30 hours. A clear, viscous liquid is obtained. pH: 8.9; K value: 10.5.
• 8. 225.6 g (2.4 mol) of phenol are melted in a 1-1 four-necked flask with a nitrogen blanket at 50-60.degree. Then 117.6 g (1.2 mol) of concentrated sulfuric acid are added dropwise with stirring over a period of about 30 minutes, the temperature rising to a maximum of 100.degree. Then 123 g (1.1 mol) of chlorobenzene are added and the mixture is boiled on a water separator (internal temperature about 135 ° C.). The heavy phase (chlorobenzene) runs back into the flask. After 41 g of water have been distilled off, the mixture is cooled to 90 ° C., the water separator is exchanged for a separator for solvents which are heavier than water, the distilled water and another 100 g of deionized water are added to the reaction mixture and the chlorobenzene is removed from the mixture. In the course of the chlorobenzene distillation, a further 100 g of deionized water are run in. When all the chlorobenzene has been separated off, 100 g of water are distilled off. The mixture is cooled to 70 ° C. and 146 g (1.2 mol) of 33% sodium hydroxide solution are metered in. Then 108 g (1.08 mol) of 30% formaldehyde solution and finally 72 g (0.24 mol) of 40% sodium sulfamate solution are added dropwise. Subsequent heating at reflux for ten hours gives a red-brown viscous liquid.

Application engineering examples For example 1.

The product thus obtained was applied to polyamide carpet yarn as described in the exhaust process with 2.5% (0.8% active substance), based on the weight of the goods. The pH was adjusted to 3.5 and 2 with amidosulfuric acid. When the blocking effect was tested, it was found that a slight staining was found at pH 3.5, but no staining at pH 2, while untreated control goods were dyed deep red. Samples treated with this product show no yellowing after 16 hours of UV radiation in the Xenotest.

For example 3.

In the exhaust process, the solution thus obtained was applied to polyamide carpet yarn with 2.5% (1% active substance), based on the weight of the goods, at a pH of 3.5 adjusted with acetic acid as described. The yarn treated in this way was tested for protection with the method described. The finished strand showed only a slight staining, while the untreated control goods were stained deep red. Samples that were treated with this solution show no yellowing after 16 hours of UV radiation in the Xenotest.

For example 5.

As in the previous application example, the solution thus obtained was applied to polyamide carpet yarn with 2.5% (1% active substance), based on the weight of the goods, at a pH of 3.5 set with acetic acid and then tested for the tendency to soiling. The finished strand showed a slight staining, while the untreated control goods are stained deep red. Samples that were treated with this solution show no yellowing after 16 hours of UV radiation in the Xenotest.

Claims (3)

1. A process for the dirt-repellent finishing of textile material made of wool or polyamide, characterized in that the textile material with a condensation product of a dinuclear phenol of the formula 1

where X is a direct bond or a bridge member of the formula -S0 ₂ -, -SO-, -S-, -CH ₂ -, -C (CH ₃ ) ₂ - or -CO-, preferably -S0 ₂ -, n and n 'are the numbers 1 or 2, m and m' are the numbers 0, 1 or 2 and Me is hydrogen or an alkali metal, alkaline earth metal or ammonium ion, with formaldehyde and amidosulfuric acid, or their alkali metal, alkaline earth metal or Treated ammonium salts. 2. The method according to claim 1, characterized in that the textile material is treated with a condensation product of a dinuclear phenol of the formula 1, wherein X is a bridge member of the formula -S0 ₂ -, with formaldehyde and amidosulfuric acid or its alkali metal, alkaline earth metal or ammonium salt . 3. The method according to claim 1, characterized in that 0.2 to 5 wt .-% of the condensation product is applied to the textile material.