DE10040631A1 - Yellowing inhibitor for blue denim textiles - Google Patents

Abstract

The invention relates to the use of condensed or uncondensed sulfonated aromatic compounds, monomeric, oligomeric or polymeric aromatic sulfones or sulfonic acids and/or monomeric, oligomeric or polymeric aromatic sulfone derivatives or sulfonic acid derivatives for stabilizing textile products or fabrics that are dyed with indigo or indigo derivatives against yellowing. When sulfonated diaryl sulfone derivatives are used, the degree of sulfonation, based on an aryl monomer, ranges from 0.5 to 3. The preferred agents are diphenylsulfone or diphenylsulfone derivatives of the general formula (I), wherein R<1> to R<10> are the same or different and are selected from H, OH, an alkyl, hydroxyalkyl, carboxylic acid, sulfonated or unsulfonated aryl group, an SO3H group or epoxy group, wherein at least one of the residues R<1> to R<10> is an SO3H group and at least one of the residues R<1> to R<10> is an OH group or a carboxyl group. Further preferred compounds are naphthalenesulfonic acid, naphthalenesulfonate or a respective condensation product thereof that has a degree of sulfonation, based on one naphthalene unit, that ranges from 0.5 to 7.

Description

The invention relates to the use of condensed or non-condensed sulfonated aromatics, diarylsulfone and / or monomeric, oligomeric or polymeric diarylsulfone derivatives for stabilizing dyed textile or Fabrics against yellowing and the attack of ozone and a corresponding Process for treating the dyed textile or fabric and the behan Delte textile goods or fabric itself. The textile goods can, for example, in shape of yarns, knitted fabrics or nonwovens and, like the fabric, in the form of ready-made goods are available.

Dyed textile goods or fabrics, in particular indigo dyed textile goods or fabrics, from which denim clothing articles, and in particular denim clothing articles with a stone-wash look, are produced, tend to yellowing due to the oxidation of indigo in the air. This is noticeable in the shipping and storage of textile retailers as a color change on the outside of stacks of goods. The denim articles then show bright edges, since only these are directly exposed to the effect of the surrounding atmosphere when stored in a stack. For the oxidation of indigo to the responsible for the yellowing of isatin or other colorless compounds are air pollutants, above all, such as ozone and nitrogen oxides (NO _x) responsible, made literally.

Various approaches to textile goods have become known in the prior art or fabrics, especially indigo-dyed textiles, against yellowing to stabilize taping. DE-A-196 03 401 proposes a method in which Pe roxides can be used to stabilize textiles dyed with indigo.

In DE-A-44 37 890 the textile material dyed with indigo is mixed consisting essentially of a fatty acid condensation product and a wax type treated for hydrocarbon.

In yet another prior art according to DE-A-195 37 240 a Solution of the yellowing problem suggested that the colored Tex tilgut is treated with a polyurethane. This polyurethane can be used in one dissolved organic solvent or applied in an aqueous dispersion become.

Based on this prior art, the present invention Task, connections or connection classes and a method To provide, with which the yellowing of dyed textile and fabric, esp special of indigo-dyed textile goods and fabrics, reliable and over a long period of time can be prevented.

This object is achieved by the use of condensed or uncondensed sulfonated aromatics, diarylsulfone and / or monomeric, oligomeric or polymeric diarylsulfone derivatives. The use of these classes of compounds is particularly important for the stabilization of made-up indigo-dyed textile goods or fabrics against yellowing. Such with indigo-dyed textiles are particularly sensitive to ozone and / or nitrogen oxides, which are each contained in traces in the air. Even quantities of, for example, 50 mg ozone per m ^{3 of} air lead to a strong yellowing of the dyed textiles with a storage time of about 4 weeks, which then can no longer be sold or can only be sold with a considerable loss in profit.

Such diarylsulfone derivatives are preferred among the diarylsulfone derivatives used that have been sulfonated. Sulfonated dia are particularly preferred rylsulfone derivatives with a degree of sulfonation, based on an aryl monomer, from 0.5 to 3.

Of the diarylsulfones and their derivatives, in particular diphenyl sulfone and its derivatives of the general formula (I)

to call. R ¹ to R ^{10 are the} same or different and are selected from H, OH, an alkyl, hydroxyalkyl, carboxylic acid, sulfonated or non-sulfonated aryl residue, an SO ₃ H and an epoxy group.

As the simplest compound of the aforementioned class of compounds, diphenyl sulfone, hereinafter also referred to as the diphenyl sulfone backbone, can be used. This compound results when R ¹ to R ¹⁰ in the general formula (I) are hydrogen.

Particularly good results are obtained in the stabilization of textile goods or fabrics by using sulfonated diphenyl sulfones or sulfonated hydroxydiphenyl sulfones. Then at least one of the radicals R ¹ to R ¹⁰ denotes an SO ₃ H group, preferably one of the radicals R ² to R ⁵ and / or R ⁶ to R ⁹ denotes an SO ₃ H group and R ¹ and / or R ¹⁰ then mean OH. However, it is expedient to esterify the OH group (s) of the hydroxydiphenyl sulfone, in which case a carboxylic acid radical in the general formula (I) stands for R ¹ and / or R ¹⁰ instead of H. In the sulfonation, methylene sulfonic acid groups or methyl sulfates can also be formed if at least one of the radicals R ¹ to R ^{10 of} the compound to be sulfonated has a corresponding methylol group.

The (hydroxy) diphenyl sulfone backbone can be substituted in many ways with regard to the aromatics. If R ¹ to R ^{10 are} selected from alkyl, hydroxy alkyl and sulfonated or non-sulfonated aryl residues, the following applies with regard to the chain length of the alkyl or hydroxyalkyl groups to be observed and with regard to the aryl residues, among those in connection with the present invention also condensed aromatics are to be understood as a limiting selection criterion that they must be selected so that the substituted (hydroxy) diaryl or (hydroxy) diphenyl sulfone derivative maintains a planar structure. It follows that branched alkyl radicals are possible in principle, but can only be used to a limited extent with regard to their degree of branching.

Of the sulfonated aryl radicals, the naphthalene sulfonate in particular is to be named, which can form at least one of the radicals R ¹ to R ¹⁰ or R ² to R ⁵ and / or R ⁶ to R ⁹ . The aromatics or condensed aromatics can also be selected as desired in such a way that their installation in the basic structure does not result in any steric hindrance which could result in the deviation from a planar basic structure.

For the use according to the invention of the claimed diaryl or hydroxy diaryl or diphenyl or hydroxydiphenyl sulfone derivatives, oligomeric or polymeric diaryl or hydroxydiaryl or diphenyl or hydroxydiphenyl sulfone derivatives are also suitable in addition to the monomers. It is advantageous for the oligomeric or polymeric linkage if at least one of the radicals R ¹ to R ¹⁰ or R ² to R ⁵ and / or R ⁶ to R ^{9 is} a hydroxyalkyl group. The oligomeric or polymeric linkage is then achieved via the hydroxyl function of the corresponding hydroxyalkyl group, as shown below in formula (II). The choice of R ⁷ in the form of a hydroxymethyl group, put in formula. The selection of R ⁷ in the form of a hydroxymethyl group, represented in formula (II) as a (condensed) methylene group, is exemplary and is merely illustrative in nature, without restricting the oligomeric or polymeric structures claimed. The linkage shown here of the radical R ⁷ with the second monomer via R ^{4 is} equal to H of the second monomer, as shown below, has only illustrative character. There are also other link mechanisms known per se to the person skilled in the art with one of the radicals R ¹ to R ¹⁰ or R ² to R ⁵ or R ⁶ to R ⁹ , in which these radicals are not equal to hydrogen.

Preferably the condensation reaction is used to form the oligome ren or polymeric structures in the presence of formaldehyde leads, when terminating the condensation reaction hydroxyalkyl end groups or methylols as end groups of the oligomers or polymers formed are particularly suitable.

However, not only those previously used for the use according to the invention diaryl or diphenyl sulfone compounds described in more detail as suitable showed, but also condensed or uncondensed sulfonated aroma Ten. In particular, naphthalenesulfonic acid or naphthalenesulfonate  name that already as a substituent in connection with the diarylsulfone derivatives has been mentioned.

The preferred degree of sulfonation is 0.5-7, based on a naphtha lineinheit. The degree of sulfonation becomes independent of the respective condensate degree related to a naphthalene unit. Highly condensed aromatics can contain correspondingly more sulfo groups.

It has been shown that the condensed or uncondensed sulfonators ten aromatics can be selected in such a way that the end selection criterion of an essentially planar structure is met. Corresponding can the condensed or uncondensed sulfonated aromatics, and here in particular naphthalenesulfonic acid or naphthalenesulfonate any sub have substituents, with the proviso that these be no steric hindrance things that deviate from an essentially planar basic structure could entail.

The invention also relates to a method for stabilizing colored text tilgut or tissue against yellowing and the attack of ozone, in which the ge dyed textile goods in aqueous solution with a condenser explained above th or uncondensed aromatics, diarylsulfone or diarylsulfone derivative will act.

The blue denim fabric to be treated, or the jeans, is in aqueous solution solution, in an acidic medium at a pH of 2-7, preferably 3-4 and at Temperatures of 30-100 ° C, preferably 70-80 ° C, with the invention eats connections. The pH can be adjusted with any mineral or organic acids can be adjusted. Formic acid or Hydroethane diphosphonic acid used. The duration of treatment is preferred wise 10 min. The concentration of the compounds according to the invention in Treatment bath is 0.1-10%, calculated as dry matter and related on the weight of the textile goods or fabric to be stabilized. Subsequently is the excess at the respective by repeated rinsing with water  by repeatedly rinsing with water, the excess of the one used removed compound of the invention and the textile preferably at 120 ° C. dried.

Then the textile or the jeans with a selected fatty acid condensate can be softened. To adjust the pH of the soft permanent non-volatile acid is preferably used, such as B. citric acid.

The invention also relates to dyed textile goods or fabrics, in particular Textile or fabric dyed with indigo that is condensed or not condensed sulfonated aromatics, a diarylsulfone and / or a diarylsulfone has derivative according to one of the embodiments explained above.

The invention is explained in more detail below with the aid of examples, the presented and used in accordance with the invention simplifying connections are briefly called anti-yellowing agents.

Examples Anti-yellowing 1

A hydroxydiphenyl sulfone, which is commercially available under the name Diphon A, is used as the starting compound. The sulfonation of this starting compound is carried out using sulfuric acid, whereby 70 to 100 percent sulfuric acid or 5 to 30 percent oleum can be used. At the same time, acetic anhydride is added in order to convert the hydroxyl compounds of the starting compound diphone A into the corresponding acetic acid esters. The compound of formula (III) given below was obtained:

Anti-yellowing 2

Starting from yellowing inhibitor 1, a polymerization of the yellowing inhibitor 1 was carried out by adding an excess of diphone A in an acid medium and in the presence of formaldehyde in order to obtain the compound of formula (IV) given below as yellowing inhibitor 2:

It is expressly pointed out that formula (IV) is a possible one polymeric linking variant of the yellowing inhibitor 2 exemplarily Darge has been put.

Anti-yellowing 3

As another yellowing inhibitor, one became commercially available under the name Mesitol available methylene linked condensation product of arylsulfone acids and hydroxyarylsulfone used in the form of an aqueous preparation.

Anti-yellowing 4

As a yellowing inhibitor based on the condensed sulfonated aromatics was a naphthalenesulfonic acid-formaldehyde polycondensate in the form of its Sodium salt, which is called Setamol. WS is commercially available, a set.

1. Examination of anti-yellowing by fumigation Sample preparation and testing of the yellowing inhibitors by NO _x treatment

Sections of 16 × 8 cm of a blue denim fabric or jeans were made each in a polyethylene bag for food, previously in 2 rows with 12 holes / 16 cm each using a standard punch for the office had been perforated on both sides, so that 4 seams were parallel to the Perforation were formed. The front sides were also closed with seams sen.  

The samples prepared in this way were placed on a flexible stainless steel yarn carrier 5 cm in diameter and fastened with sewing thread. It was ge ensures that the gas had access to the perforation on both sides.

A commercial desiccator with a diameter of 33 cm and a volume of approx. 20 l, each with a ground joint on the side and top, was used as the fumigation device. A horizontal fan is placed horizontally in the middle on a stainless steel frame. This is a commercially available fan, as is customary for computers, with a diameter of 8 cm and a delivery rate of approx. 40 m ^3. The supply lines to the fan were inserted laterally airtight using a silicone plug, the upper ground plug was provided with a dropping funnel. A 100 ml beaker with a weighed amount of NaNO ₂ , which corresponds to the desired amount of gas, was placed on a grate above the fan under the outlet of the dropping funnel.

Five samples previously conditioned in the climatic cabinet for 24 hours in a standard climate were placed around the fan in the center of the desiccator and the desiccator closed. 70% sulfuric acid was added to the dropping funnel (multiple excess to NaNO ₂ ). The fan was activated, the sulfuric acid was added to the beaker by opening the dropping funnel and the desiccator was then closed again.

Gas concentrations and fumigation times

Since the tendency to yellowing varies from product to product and depends on many unknown parameters, preliminary tests with different gas concentrations and times must first be carried out for unknown materials. The following concentrations and times were used:
8 and 16 ml / l NO ₂
7.5, 15 and 30 min fumigation time.

Evaluation of the tests carried out

The assessment must be carried out immediately after fumigation, as a Post-yellowing cannot be ruled out. This is done by wrapping the film around the perforation removed from the test object by means of a razor, the 3 most yellowed Points are selected using a gray scale to determine the Color change assessed according to DIN 54001 and the results averaged. So he you keep grades from 1 to 5, where 1 is a very strong yellowing and 5 none at all Mean yellowing.

Blue denim textile used

A raw, elastic blue denim was used, as it is known is that it tends to yellow. This blue denim textile was made in Tube shape sewn on large machines in a laundry using Amylase desized and then using a commercially available, acidic cellulase gestont. No stones were used. Then was ge flushes. The usual washing and bleaching with chlorine was used waives, since it has been shown in practice that especially materials made of fashion reasons are kept dark, very susceptible to the camp Virgil are exercise. In addition, this procedure uses the normally bright shot very strong thread on the inside with the detached indigo / cellulose particles soiled, which yellow much faster due to the delicacy and so with another evaluation option. Basically everyone can articles dyed with indigo can be used, provided they no longer have a size contains. Finishing based on starches or plastics on the warp thread are applied, prevent or slow down the yellowing, so that this practically does not occur. No case has become known in which raw chair goods are yellowed. The envelope makes the access for gases to the Indigo dye practically impossible.  

Testing of anti-yellowing by ozone treatment

In the case of ozone treatment, the suitably equipped blue denim textiles were not treated in perforated film, as in the case of nitrogen oxide treatment, but the lightening was determined as a whole and using colorimetry for the samples used. Similar to the gray scale, these values were converted into notes. A yellow color is not obtained with ozone, indigo is broken down to colorless components, but the cotton underneath is often not fully bleached, which is why depending on the exposure time (ozone also has a bleaching effect), yellow to white areas are obtained, but never as intensely yellow as at NO _x . For this reason, both values can only be compared, but not directly.

The evaluations of the test results show that the method according to the invention is effective both against ozone and against NO _x .

The test results are summarized in Table 1 below.  

Table 1

II. Investigation of the anti-yellowing by the display method

As a further experiment, the so-called spreading method was carried out; H. it was the corresponding samples in exposed areas, if possible with high air circulation and high pollutant content of the air, designed with parts through Foils were covered and after a long storage period of at least 1 month to 3 months by evaluating the color depth differences between the covered and the ventilated parts were evaluated. This test also passes made the differences found in Table 1. Not with the inventions Jeans equipped with anti-yellowing agents were after 3 weeks already clearly (visually visible) yellowed, the equipped ones after 3 months in original condition.

Claims (15)

1. Use of condensed or uncondensed sulfonated A romates, diarylsulfone and / or monomeric, oligomeric or polymeric Diarylsulfone derivatives for stabilizing dyed textile or Fabrics against yellowing and the attack of ozone. 2. Use according to claim 1 for the stabilization of colored with indigo Textile or fabric. 3. Use according to claim 1 or 2, characterized by sulfonated Diarylsulfonderivate. 4. Use according to claim 3, characterized in that the sulfonia degree, based on an aryl monomer, is 0.5-3. 5. Use according to one of claims 1 to 4, characterized by diphenyl sulfone or diphenyl sulfone derivatives of the general formula (I):
wherein R ¹ to R ^{10 are the} same or different and selected from H, OH, an alkyl, hydroxyalkyl, carboxylic acid, sulfonated or non-sulfonated aryl residue, an SO ₃ H and an epoxy group. 6. Use according to claim 5, characterized in that at least one of the radicals R ¹ to R ^{10 is} a SO ₃ H group. 7. Use according to claim 5 or 6, characterized in that at least one of the radicals R ¹ to R ¹⁰ , preferably at least one of the radicals R ¹ or R ^{10 is} an OH or carboxyl group. 8. Use according to one of claims 5 to 7, characterized by oligomeric or polymeric diphenylsulfone derivatives, starting from the compounds of the general formula (I), wherein at least one of the radicals R ¹ to R ¹⁰ denotes a hydroxyalkyl group. 9. Use according to claim 1 or 2, characterized in that as condensed sulfonated aromatic naphthalenesulfonic acid, naphthalenesul fonat or a condensation product thereof is used. 10. Use according to claim 9, characterized in that the sulfonia degree, based on a naphthalene unit, is 0.5-7. 11. Process for stabilizing dyed textile and fabric against Yellowing and the attack of ozone, characterized in that the Textile or fabric in aqueous solution with a condensed or uncondensed sulfonated aromatics, diarylsulfone or a slide rylsulfone derivative is treated according to one of claims 1 to 10. 12. The method according to claim 11, characterized in that the pH of the aqueous solution to a value between 2 to 7, preferably between 3 to 4. 13. The method according to claim 11 or 12, characterized in that the Treatment at a temperature of 0 to 100 ° C, preferably 20 to 100 ° C and particularly preferably from 70 to 80 ° C, is carried out.   14. The method according to any one of claims 11 to 13, characterized in that the concentration of the condensed or uncondensed sulfo nated aromatics, diarylsulfones or diarylsulfone derivatives 0.1 to 10%, calculated as dry matter and based on the weight of the too stable textile or fabric. 15. Dyed textile or fabric, in particular tex dyed with indigo tilgut or tissue that has a condensed or uncondensed sul formulated aromatics, a diarylsulfone and / or a diarylsulfone derivative according to one of claims 1 to 10.