DE10222978A1 - Process for reductive post-cleaning of textile materials - Google Patents

Abstract

Process for the reductive post-cleaning of fabrics under acidic conditions, characterized in that DOLLAR A a) one or more sulfinic acids of the general formulas Ia to Ic, DOLLAR AR · 4 · O (CR · 1 · R · 2 ·) ¶m¶SO ¶2¶MN (R · 3 ·) ¶3-p¶ [(CR · 1 · R · 2 ·) ¶m¶SO¶2¶M] ¶p¶ DOLLAR AN (R · 3 ·) ¶3-qr ¶ [(CR · 1 · R · 2 ·) ¶m¶SO¶2¶M] ¶q¶ [(CR · 1 · R · 2 ·) ¶n¶SO¶3¶M] ¶r¶, DOLLAR A in which the variables are defined as follows: DOLLAR AR · 1 ·, R · 2 ·, R · 4 · the same or different and independently of one another DOLLAR A hydrogen, DOLLAR AC¶1¶-C¶6¶-alkyl such as methyl, ethyl , n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C¶1¶-C¶4¶-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl , sec.-butyl and tert.-butyl, DOLLAR AR · 3 · identically or differently and independently of one another selected from DOLLAR A Wasse rstoff, DOLLAR AC¶1¶-C¶18¶-alkyl, DOLLAR AC¶3¶-C¶12¶-cycloalkyl, unsubstituted or substituted by one to three C¶1¶-C¶4¶-alkyl radicals, DOLLAR AM the same or different and selected from equivalents of DOLLAR A ammonium ions, alkali metal ions, alkaline earth metal ions, DOLLAR A m, n 1 or 2, DOLLAR A p 1, 2 or 3, DOLLAR A q 1 or 2; where if q = 1, r = 2; and in the event that q = 2, r = 1 is selected, DOLLAR A where, in the case that m is 0, p assumes the value 2; DOLLAR A and wherein in formula Ia at least one of the radicals R · 1 ·, R · 2 ·, R · 4 · is a ...

Description

• a) eine oder mehrere Sulfinsäuren der allgemeinen Formeln I a bis I c
  
  R⁴O(CR¹R²)_mSO₂M I a
  
  N(R³)_3-p[(CR¹R²)_mSO₂M]_p I b
  
  N(R³)_3-q-r[(CR¹R²)_mSO₂M]_q[(CR¹R²)_nSO₃M]_r I c
  
  in denen die Variablen wie folgt definiert sind
  R¹, R², R⁴ gleich oder verschieden und unabhängig voneinander Wasserstoff,
  C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl,
  R³ gleich oder verschieden und unabhängig voneinander ausgewählt aus
  Wasserstoff,
  C₁-C₁₈-Alkyl,
  C₃-C₁₂-Cycloalkyl, unsubstituiert oder substituiert durch ein bis drei C₁-C₄-Alkylreste,
  M gleich oder verschieden und gewählt aus Äquivalenten von
  Ammoniumionen, Alkalimatallionen, Erdalkalimetallionen;
  m, n 1 oder 2
  p 1, 2 oder 3
  q 1 oder 2; wobei für den Fall, dass q = 1 ist, r = 2 ist; und für den Fall, dass
  q = 2 ist, r = 1 gewählt wird.
  wobei für den Fall, dass m gleich 0 ist, p den Wert 2 annimmt;
  und wobei in Formel I a mindestens einer der Reste R¹, R², R⁴ ein C₁-C₆-Alkyl ist,

und weiterhin

• a) mindestens einen Puffer und
• b) mindestens ein Tensid oder
• c) mindestens ein Dispergiermittel

einsetzt. The present invention relates to a process for the reductive aftertreatment of textile materials under acidic conditions, characterized in that

• a) one or more sulfinic acids of the general formulas I a to I c
  
  R ⁴ O (CR ¹ R ² ) _m SO ₂ MI a
  
  N (R ³ ) _3-p [(CR ¹ R ² ) _m SO ₂ M] _p I b
  
  N (R ³ ) _3-qr [(CR ¹ R ² ) _m SO ₂ M] _q [(CR ¹ R ² ) _n SO ₃ M] _r I c
  
  in which the variables are defined as follows
  R ¹ , R ² , R ^{4 are} identical or different and are independently hydrogen,
  C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl,
  R ^{3 are the} same or different and are selected independently
  Hydrogen,
  C ₁ -C ₁₈ alkyl,
  C ₃ -C ₁₂ cycloalkyl, unsubstituted or substituted by one to three C ₁ -C ₄ alkyl radicals,
  M the same or different and selected from equivalents of
  Ammonium ions, alkali metal ions, alkaline earth metal ions;
  m, n 1 or 2
  p 1, 2 or 3
  q 1 or 2; where if q = 1, r = 2; and in the event that
  q = 2, r = 1 is selected.
  where p is 2 when m is 0;
  and wherein in formula I a at least one of the radicals R ¹ , R ² , R ^{4 is} a C ₁ -C ₆ alkyl,

and still

• a) at least one buffer and
• b) at least one surfactant or
• c) at least one dispersant

starts.

Furthermore, the invention relates to formulations which in Process according to the invention advantageously as an aftertreatment agent can be used for colored textiles.

Cellulose dyeing is usually used in cellulose dyeing Textiles dyed by using suitable dyes in a strongly alkaline Environment through reducing agents in their soluble leuco form are transferred, which after penetrating into the fiber Air oxidation is converted back into the insoluble dye. As Reducing agent is mostly sodium dithionite Application, but also the use of sulfinates from GB-3-829 177 known for related printing applications. Mixtures of dithionite with sulfinates or sulfonates are described in US 3,265,459 or US 3,645,665 and US 3,798,172 as reducing agents used for cellulose dyeing.

Textiles containing polyester, on the other hand, are colored exclusively in an acidic environment. It is either after High temperature pull-out process, the thermosol process or the Superheated steam fixation procedure. In the former process the textile in the dyebath at a pH of about 3-6 and a temperature of approx. 120-140 ° C initially in one Colored pressure vessel. During this treatment the diffuses Disperse dye in the soaked polyester fiber and lies then molecularly distributed in the polymer matrix. After completion The dyeing step is usually precleaned with Fresh water and finally an alkaline, reductive Post-cleaning in the washing bath, usually using sodium dithionite and caustic soda can be used in aqueous solution.

Both in the thermosol process and in Hot steam fixation process also becomes an alkaline, reductive cleaning performed.

As in the high-temperature pull-out process, thermosol and in the steam fixation process as an aftertreatment agent usually an aqueous solution of caustic soda and Sodium dithionite used. The pH of the post-cleaning bath is therefore high and is around 12-13. Washing baths, which Na-hydroxymethanesulfinate (Rongalit®, Superlite®) optionally in mixtures with Na hydroxymethanesulfonate or Contain dithionite-formaldehyde condensates and which in In individual cases also by adding strong organic or inorganic Acids can be acidified in Japanese Writings JP-A 05 272 075, JP-A 02 300 391, JP-A 04 146 279, JP-A 01 028 090, JP-A 02 091 285, JP-A 57 006 188, JP-A 57 066 189, JP-A 60 162 889 listed. However, these washing systems are does not live up to the high demands placed on it Post-treatment agent with regard to achieving high color fastness polyester-containing textile materials.

• - hoher Zeit-, Wasser- und Energieeinsatz durch die Umstellung des pH-Werts von sauer nach alkalisch
• - hohe Salzfrachten im Färbereiabwasser sowie Farbstoffreste, welche dieses färben
• - hohe Selbstentzündlichkeitsneigung von Hydrosulfit in Substanz sowie
• - eine relativ schnelle Erschöpfung des reduktiven Waschbades durch Luftoxidation.

Disadvantages of the conventional high-temperature pull-out process are

• - high use of time, water and energy by changing the pH from acid to alkaline
• - high salt loads in the dyeing waste water as well as dye residues that dye it
• - High self-ignition tendency of hydrosulfite in substance as well
• - A relatively quick exhaustion of the reductive wash bath by air oxidation.

There are disadvantages in thermosol and hot steam fixation processes to be seen in the lack of air stability of the washing baths, so that an exact dosage of the reducing agent without significant analytical effort in the company can not be accomplished. As a result, the White Fund can become contaminated do not always avoid dye residues that have not been completely destroyed.

WO 98/03725 discloses a process for the reductive post-cleaning of dyed or printed polyester-containing textiles, in which a sulfinic acid compound, for example N (CH ₂ SO ₂ Na) ₃ or HO-CH ₂ SO ₂ Na, is an acid-binding substance, wherein the acid-binding substance is sufficient to increase the pH of the dyeing liquor or the washing bath by 1 to 3 units, and optionally a sulfonic acid compound, for example of the formula N (CH ₂ SO ₃ Na) ₃ , and optionally a surfactant are used. As an example, the process is carried out at pH values above 5, see Examples 7-17. As a process variant in the presence of surfactants, in particular a process using Tamolen® in the absence of sulfonic acid compounds N (CH ₂ SO ₃ Na) ₃ at a pH of 5 is disclosed (Examples 9a / 9b). The treated textiles show good behavior with regard to bleeding, but this can still be improved.

There was therefore the task of an improved method for To provide liquor dyeing of textiles containing polyester, in which is an elaborate intermediate rinse and a separate one Post-cleaning is eliminated, which is a time, water and Saving energy means. Undyed, low-salt waste water should continue result and that in the dye liquor or in the washing bath Post-treatment agents to be used are easy to handle, economical effective and easy to dose and good Possess cleaning effect. They should also be among the acidic ones Conditions of reductive post-cleaning the deposition of Dye residues can be avoided in order not to contaminate the goods to have. In addition, it was an object of the present invention the soiling of bleached cotton under acid To avoid conditions.

• a) mindestens einer Verbindung der Formel I a, I b oder I c
  
  R⁴O(CR¹R²)_mSO₂M I a
  
  N(R³)_3-p[(CR¹R²)_mSO₂M]_p I b
  
  N(R³)_3-q-r[(CR¹R²)_mSO₂M]_q[(CR¹R²)_nSO₃M]_r I c
  
  wobei die Variablen wie folgt definiert sind:
  R¹, R², R⁴ gleich oder verschieden und unabhängig voneinander Wasserstoff,
  C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl,
  R³ gleich oder verschieden und unabhängig voneinander ausgewählt aus
  Wasserstoff,
  C₁-C₁₈-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, n- Nonyl, n-Decyl, und n-Dodecyl; bevorzugt C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl,
  C₃-C₁₂-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl,
  ggf. substituiert durch ein bis drei C₁-C₄-Alkylreste; beispielhaft seien die nachfolgenden Sulfinate I b.1 bis I b.4 aufgeführt:
  
  
  wobei in den obigen Verbindungen I b.1 bis I b.4 ist R⁵ jeweils gleich oder verschieden ist und gewählt aus C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
  M gleich oder verschieden und gewählt aus Äquivalenten von
  Ammoniumionen, beispielsweise NH₄ ⁺ oder primäre, sekundäre oder tertiäre C₁-C₆-Alkylammoniumionen, deren Alkylreste Hydroxylgruppen tragen können; bevorzugt N(CH₃)₄ ⁺, HN(CH₃)₃ ⁺, H₂N⁺(CH₃)₂, H₃N⁺CH₃, H₃N⁺CH₂CH₂OH, H₂N⁺[CH₂CH₂OH]₂, HN⁺[CH₂CH₂OH]₃, CH₃NH⁺[CH₂CH₂OH]₂, n-C₄H₉NH⁺[CH₂CH₂OH]₂, ⁺, N(C₂H₅)₄ ⁺, HN(C₂H₅)₃ ⁺, H₂N⁺(C₂H₅)₂, H₃N⁺C₂H₅,
  Alkalimetallionen, beispielsweise Li, Na, K, Rb, Cs, insbesondere Na oder K-Ionen;
  oder Erdalkalimetallionen, bevorzugt Mg-Ionen oder Ca-Ionen;
  m, n 1 oder 2
  p 1, 2 oder 3
  q 1 oder 2; wobei für den Fall, dass q = 1 ist, r = 2 ist; und für den Fall, dass
  q = 2 ist, r = 1 gewählt wird.
  wobei in Formel I a mindestens einer der Reste R¹, R², R⁴ ein C₁-C₆-Alkyl ist,
  und wobei für den Fall, dass m gleich 0 ist, p den Wert 2 annimmt.

Accordingly, a process for the reductive post-cleaning of fabrics under acidic conditions has been found, which is characterized in that the fabric is treated with

• a) at least one compound of the formula I a, I b or I c
  
  R ⁴ O (CR ¹ R ² ) _m SO ₂ MI a
  
  N (R ³ ) _3-p [(CR ¹ R ² ) _m SO ₂ M] _p I b
  
  N (R ³ ) _3-qr [(CR ¹ R ² ) _m SO ₂ M] _q [(CR ¹ R ² ) _n SO ₃ M] _r I c
  
  where the variables are defined as follows:
  R ¹ , R ² , R ^{4 are} identical or different and are independently hydrogen,
  C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl,
  R ^{3 are the} same or different and are selected independently
  Hydrogen,
  C ₁ -C ₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n dodecyl; preferably C ₁ -C ₆ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec.-butyl and tert.-butyl,
  C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred,
  optionally substituted by one to three C ₁ -C ₄ alkyl radicals; the following sulfinates I b.1 to I b.4 are listed as examples:
  
  
  where in the above compounds I b.1 to I b.4 R ^{5 is in} each case the same or different and selected from C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso -Butyl, sec-butyl and tert-butyl;
  M the same or different and selected from equivalents of
  Ammonium ions, for example NH ₄ ⁺ or primary, secondary or tertiary C ₁ -C ₆ -alkylammonium ions, the alkyl radicals of which can carry hydroxyl groups; preferably N (CH ₃ ) ₄ ⁺ , HN (CH ₃ ) ₃ ⁺ , H ₂ N ⁺ (CH ₃ ) ₂ , H ₃ N ⁺ CH ₃ , H ₃ N ⁺ CH ₂ CH ₂ OH, H ₂ N ⁺ [CH ₂ CH ₂ OH] ₂ , HN ⁺ [CH ₂ CH ₂ OH] ₃ , CH ₃ NH ⁺ [CH ₂ CH ₂ OH] ₂ , nC ₄ H ₉ NH ⁺ [CH ₂ CH ₂ OH] ₂ , ⁺ , N ( C ₂ H ₅ ) ₄ ⁺ , HN (C ₂ H ₅ ) ₃ ⁺ , H ₂ N ⁺ (C ₂ H ₅ ) ₂ , H ₃ N ⁺ C ₂ H ₅ ,
  Alkali metal ions, for example Li, Na, K, Rb, Cs, in particular Na or K ions;
  or alkaline earth metal ions, preferably Mg ions or Ca ions;
  m, n 1 or 2
  p 1, 2 or 3
  q 1 or 2; where if q = 1, r = 2; and in the event that
  q = 2, r = 1 is selected.
  where in formula I a at least one of the radicals R ¹ , R ² , R ^{4 is} a C ₁ -C ₆ alkyl,
  and where, if m is 0, p takes the value 2.

Sodium sulfinates (M = Na) and particularly preferably the compounds H ₂ NCH ₂ SO ₂ Na, HN (CH ₂ SO ₂ Na) ₂ , N (CH ₂ SO ₂ Na) ₃ , HOCH (CH ₃ ) SO are preferably found in the process according to the invention ₂ Na, H ₂ NCH (CH ₃ ) SO ₂ Na, HN (CH (CH ₃ ) SO ₂ Na) ₂ , N (CH (CH ₃ ) SO ₂ Na) and sodium salts of 1-, 2-, 3-, 4- or 5-ethylhexylaminomethanesulfonic acid and -ethanesulfonic acid use.

Under acidic conditions in the sense of the present invention pH values are from 3.9 to below 5, preferably from 4 to 4.8 Roger that. The pH value can be adjusted while the inventive method in the context of measurement accuracy remain constant, d. H. change by a maximum of 0.1 units, he can but also increase and decrease or by a maximum or run a minimum.

Known from the literature are preferably used as buffers Dicarboxylic acid buffers, especially citric acid buffers, for example in the form of citric acid / alkali metal citrate solutions become. Other suitable buffers are, for example Phosphoric acid / phosphate buffer, Eulysin® S buffer or Acetic acid alkali metal acetate buffer or mixtures of at least two of the buffer mentioned above.

Preferred surfactants are alkoxylation products which based on aliphatic or alkyl aromatic hydroxy, amine and aminohydroxy compounds under the brand names Synperonic® and Ukanil®, Dehypon®, Neopol® ethoxylates, Emulan®, Lutensol®, Plurafac® and Pluronic® or Elfapur® commercially available are used. Are particularly well suited Ethoxylation products based on castor oil, oleic acid or Tallow. The degree of ethoxylation is between 3 and 60, preferably between 10 and 50 ethylene oxide units.

Other preferred surfactants are:
Polyalkylene glycols, known under the brand names Pluriol® and Antarox®,
aliphatic and alkyl aromatic single and multiple sulfonates with the brand names Lutensit®, Rhodacar®, Rhodapon® and Teepol®,
Acid esters and amides such. B. sulfosuccinic acid ester of the brand Elfanol®,
Phosphoric acid partial esters, which are sold under the names Rhodafac® or Marlophor®,
Fatty acid partial glycerides and fatty acid alkanolamides, which can be obtained under the brand names Luwitor® or Marlamid®,
as well as the surfactants offered under the names Plantaren® and Glucopon®.

Furthermore, surfactants with betaine or Sultain groups are used to find out which inner salts quaternary ammonium and carboxylate (betaine) or sulfonate (Sultain) ion are and z. B. available under the brand name Mackam® are. Furthermore, cationic surfactants can also be used quaternary ammonium compounds and amine oxides are used as they are for example under the names Alkaquat® and Rhodaquat® and Mackalene®, Mackernium®, Mackpro® and Mackamine® are offered.

The following are advantageously used as dispersants: Polycarboxylates and copolymers which, for. B. under the brand name Sokalan® or Elvacite®, or so-called "hyperdispersants", which are sold under the name Solsperse® Condensates based on aromatic or alkylaromatic sulfonates, under the brand names Tamol® and Nekal® as well as Supragil® and Rhodacar® are available.

• 1. a liegt zwischen 0 und 180, bevorzugt zwischen 0 und 125
• 2. b liegt zwischen 20 und 180, insbesondere zwischen 35 und 125, wobei b ≥ a ist;
  M ist ein Alkalimetall, bevorzugt Na oder K und besonders bevorzugt Na;
  d ist 0 oder 1.

Oxalkylated phenols are particularly preferred. Partially neutralized sulfated oxyalkylated phenols of the general formulas III and IV are very special


or their mixtures, in which the variables are defined as follows:

• 1. a is between 0 and 180, preferably between 0 and 125
• 2. b is between 20 and 180, in particular between 35 and 125, where b ≥ a;
  M is an alkali metal, preferably Na or K and particularly preferably Na;
  d is 0 or 1.

Compounds III and IV are advantageously prepared by reacting phenols V and VI, respectively


with propylene oxide and subsequent reaction of the adduct with ethylene oxide or by reacting V or VI with ethylene oxide. The adducts can then be completely or partially reacted with chlorosulfonic acid or sulfur trioxide to give half-sulfuric acid and the resulting half-esters neutralized with alkaline agents.

The phenols of the formulas V and VI can be obtained by reacting bisphenol A (2,2- (p, p'-bishydroxydiphenyl) propane) or phenol with 4 or 2 mol of styrene in the presence of acid as a catalyst. The known phenols V and VI are first used with known processes using propylene oxide and then with ethylene oxide or only with ethylene oxide in the presence of acidic or alkaline catalysts, for example with NaOCH ₃ or SbCl ₅ , to give the corresponding oxyalkylation products III and IV with d = 0 implemented. The oxyalkylation can e.g. B. by the method described in US 2,979,528.

The sulfuric acid semiesters are obtained by reaction of the Oxalkylation products with chlorosulfonic acid or sulfur trioxide prepared, the amount of chlorosulfonic acid or sulfur trioxide is chosen so that all free hydroxyl groups or only one certain percentage is sulfated. In the latter case form mixtures of compounds of formula III or IV, the free and contain sulfated hydroxyl groups. For use as Dispersants are those obtained from the reaction Half-ester of sulfuric acid converted into water-soluble salts. As such come advantageously the alkali metal salts, for. B. the Sodium or potassium salts. In the case of Chlorosulfonic acid two equivalents, one for sulfur trioxide Equivalent basic compounds required. As the latter one expediently uses aqueous alkali metal hydroxide. During neutralization, the temperature should not be 70 ° C exceed. The salts obtained can be in the form of aqueous Solutions or isolated as such and used in solid form become.

Dispersants III are preferred in which a is from 0 to Average 2.5, b average 25 to 250 and d 0 to average 0.5. Dispersants III in which a is 0 are particularly preferred to an average of 2.5, b an average of 50 to 100 and d an average of 0.5 is.

Numerous representatives of compounds III and IV are known and z. B. described in US 4,218,218.

Other particularly preferred dispersants are by Sulfonating aromatic compounds such as naphthalene itself or Mixtures containing naphthalene and subsequent condensation of the naphthalenesulfonic acids or arylsulfonic acids formed Formaldehyde available.

As a starting product for the production of arylsulfonic acids for example the mixture characterized in Table 1 aromatic compounds used by thermal cleavage of a naphthenic residual oil at a temperature of 1400 to 1700 ° C and fractionation of the fission products (fraction at 1013 mbar, 100-120 ° C passing) was obtained. These naphthenic Residual oils accumulate when cracking light petrol and become also as high-boiling aromatic hydrocarbon oils designated.

This aromatic fraction consists of a mixture of many aromatic substances, the structure and amount of which can practically not be determined in detail. The following aryl compounds are the most important representatives of this aromatic fraction: Table 1

The aromatic fraction also contains identified Ingredients in amounts from 0.1 to about 2% by weight of the following aromatic Compounds: fluorene, indane, α-methylstyrene, phenanthrene, Methyl indane, dimethyl naphthalene, ethyl naphthalene isomers, Xylene isomers, tetralin, styrene, methylethylbenzene, anthracene, Fluoranthrene, pyrene and toluene.

The production of dispersants based on sulfonated Aromatic fractions can be in the presence of aromatic or long-chain aliphatic carboxylic acids, their salts, anhydrides or mixtures of these compounds can be made.

Examples of suitable aromatic carboxylic acids or their Derivatives are naphthalene carboxylic acid, phthalic acid, Terephthalic acid, isophthalic acid, benzoic acid, trimellitic acid, Phenylacetic acid, phenoxyacetic acid, salicylic acid, p-hydroxybenzoic acid, Diphenylacetic acid, m-hydroxybenzoic acid, benzene tetracarboxylic acid or acid anhydrides such as trimellitic anhydride, Benzene-1,2,4,5-tetracarboxylic acid dianhydride or Phthalic anhydride.

Suitable long-chain aliphatic carboxylic acids are in particular saturated or olefinically unsaturated, linear or branched aliphatic monocarboxylic acids with 8 to 22, preferably 8 to 18 Carbon atoms of natural or synthetic origin, for example higher fatty acids such as lauric acid, myristic acid, Palmitic acid, stearic acid, oleic acid, linoleic acid or Linolenic acid or synthetically produced carboxylic acids such as 2-ethylhexanoic acid, isononanoic acid or isotridecanoic acid.

The salts of the carboxylic acids mentioned are the alkali, Ammonium or alkaline earth salts are considered, for example by neutralizing these carboxylic acids with sodium hydroxide solution, Potash lye, lithium hydroxide, soda, magnesium carbonate, calcium oxide, Calcium hydroxide, ammonia or alkanolamines such as ethanolamine, Diethanolamine or triethanolanine are available.

Sodium benzoate, sodium phenylacetate, Sodium salicylate, sodium 4-hydroxybenzoate, sodium terephthalate, Sodium 2-hydroxy-3-naphthalenecarboxylate Naphthalene-1-carboxylic acid, phthalic anhydride or benzoic acid.

In this case, suitable dispersants are in particular those Mixtures containing 50 to 97% by weight, in particular 70 to 95% by weight, Arylsulfonic acid-formaldehyde condensation products and 3 to 50% by weight, in particular 5 to 30 wt .-%, aromatic or long-chain aliphatic carboxylic acids, their salts or anhydrides or mixtures thereof.

These mixtures are sulfonated in the first step by reaction with concentrated sulfuric acid or with oleum with an SO ₃ content of 10 to 65% by weight, at temperatures of 120-160 ° C., preferably at 135-145 ° C. 0.7 to 1.5 parts by weight of oleum with 65% by weight of SO ₃ or a corresponding amount of oleum with a lower SO ₃ content are advantageously used per part by weight of the aromatics. The reaction time at 145 ° C is usually from 1.5 to 3 hours, at 140 ° C from 2R to 4 hours and at 135 ° C from 3R to 6 hours.

After sulfonation, the arylsulfonic acid mixtures contain at least 50% by weight of a mixture of α- and β-naphthalenesulfonic acids, the ratio of the α- to the β-isomers is usually 20: 1 to 1: 8, in particular 10: 1 to 1: 5 and completely is particularly preferably 1: 1 to 1: 2.

Then the sulfonated products with formaldehyde condensed. This is generally done by looking at the Reaction mixture of the sulfonation reaction diluted with water and then adds formaldehyde, preferably in the form of the 10th up to 50% by weight aqueous solution. The mixture thus created lasts over a period of 4 to 12, preferably 7 to 9 hours at a temperature of 90 to 105 ° C. If you are under increased pressure works, for example from 1.1 to 10 bar, you can also at Working reaction temperatures of 105 to 150 ° C. Usually 0.03 to 0.2, preferably 0.07 to 0.17 parts by weight are used Formaldehyde, based on sulfonation products.

After completion, the reaction mixture is usually neutralized, for example with sodium hydroxide, Potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate or Sodium bicarbonate in the form of aqueous solutions until the pH is between 6 and 11.

When using the above-mentioned aromatic fraction, the condensation products have a sulfonic acid group content of at most 40% by weight. Due to the manufacturing process, up to 10% by weight of Na ₂ SO ₄ and up to 25 mol% of sulfuric acid, based on sulfonic acid groups, can still be present in the condensation products.

The dispersants described above and their Manufacturing are known and z. B. in US 5,186,846, DE-A-11 37 005 or EP-A 0 380 778.

Masking of potentially disruptive heavy metal ions or a reduction in water hardness can also be achieved by using such complexing agents. Suitable complexing agents are e.g. B. Nitrilotriacetic acid (NTA, N (CH ₂ COOH) ₃ , ethylenediaminetetraacetic acid (EDTA, [CH ₂ N (CH ₂ COCH) ₂ ] ₂ ), diethylenetriaminepentaacetic acid (DTPA, HOOCCH ₂ N [(CH ₂ ) ₂ N (CH ₂ COOH ) ₂ ] ₂ ), Hydroxyethylethylenediamine triacetic acid (HEDTA, HO (CH ₂ ) ₂ N (CH ₂ COOH) (CH ₂ ) ₂ N (CH ₂ COOH ₂ ), Propylenediaminetetraacetic acid (PDTA, (HOOCCH ₂ ) ₂ N (CH ₂ ) ₃ N (CH ₂ COOH) ₂ ) or β-alaninediacetic acid (HOOCCH ₂ ) ₂ N (CH ₂ ) ₂ COOH), which are sold under the brand name Trilon®, for example, and mixtures of these complexing agents with one another and with other acid-binding substances possible.

• a) Sulfonate der Formel II a oder II b
  
  R⁴O(CR¹R²)_mSO₃M II a
  
  N(R³)_3-p[(CR¹R²)_mSO₃M]_p II b
  
  zugegeben werden, wobei R¹, R², R³, R⁴, M, p und m dieselbe allgemeine Bedeutung wie in Formel I a bis I c besitzen, wobei die Auswahl dieser Variablen im konkreten Einzelfall für die Verbindungen der Formeln I a bis I c und II a und II b nicht gleich sein muss.

In a particular embodiment of the present invention, the method according to the invention can additionally be used

• a) sulfonates of the formula II a or II b
  
  R ⁴ O (CR ¹ R ² ) _m SO ₃ M II a
  
  N (R ³ ) _3-p [(CR ¹ R ² ) _m SO ₃ M] _p II b
  
  are added, where R ¹ , R ² , R ³ , R ⁴ , M, p and m have the same general meaning as in formulas I a to I c, the selection of these variables in the specific individual case for the compounds of the formulas I a to I c and II a and II b need not be the same.

Sodium sulfonates (M = Na) and particularly preferably the compounds H ₂ NCH ₂ SO ₃ Na, HN (CH ₂ SO ₃ Na) ₂ , N (CH ₂ SO ₃ Na) ₃ , HOCH (CH ₃ ) SO are preferably found in the process according to the invention ₃ Na, H ₂ NCH (CH ₃ ) SO ₃ Na, HN (CH (CH ₃ ) SO ₃ Na) ₂ , N (CH (CH ₃ ) SO ₃ Na) and sodium salts of 1-, 2-, 3-, 4- or 5-ethylhexylaminomethanesulfonic acid and -ethanesulfonic acid use.

The preferred molar ratio of sulfinate to sulfonate is 20: 1 to 1:20, especially 10: 1 to 1:10.

The synthesis of the compounds of general formulas II a to II b is known, see for example WO 98/03725 and the therein cited literature.

It is particularly preferred for numerous syntheses resulting mixtures of compounds of general formula I a to I c and II a and II b to use.

As a further additive, when carrying out the process according to the invention, at least one ammonium, alkali or alkaline earth metal salt selected from sulfites, hydrogen sulfites (bisulfites) or disulfites can be added. The proportion of salt in the total mixture is preferably 5-30% by weight. The alkali metal salts, in particular Na ₂ SO ₃ , NaHSO ₃ or Na ₂ S ₂ O ₅ , are advantageously added.

• 1. Umsetzungsprodukte aus gesättigten oder ungesättigten aliphatischen Carbonsäuren mit 3 bis 30 C-Atomen und aliphatischen Oligoaminen mit 2 bis 8 N-Atomen, welche zusätzlich Hydroxylgruppen tragen können, oder Dialkanolaminen oder Derivate solcher Umsetzungsprodukte,
• 2. aliphatische Sulfoniumsalze, welche durch zusätzliche hydrophile Gruppen substituiert sein können,
• 3. aliphatische oder aromatische Monocarbonsäuren und/oder Dicarbonsäuren mit 3 bis 16 C-Atomen oder deren wasserlöslichen Salzen,
• 4. Triazole oder Derivate hiervon,
• 5. Imidazole oder Derivate hiervon,
• 6. Thiazole oder Derivate hiervon,
• 7. ungesättigte aliphatische Alkohole mit 3 bis 6 C-Atomen,
• 8. Alkenylbernsteinsäure, deren wasserlösliche Salze oder Derivate solcher Alkenylbernsteinsäuren,
• 9. Polymaleinsäuren oder deren wasserlösliche Salze,
• 10. α-Olefin-Maleinsäureanhydrid-Copolymere,
• 11. Sulfamidocarbonsäuren oder deren wasserlösliche Salze.

If necessary, one or more corrosion inhibitors f) can also be added. The amounts are, depending on the type of corrosion inhibitor, of course, in the range from 1 ppm to 1% by weight, based on the mixture as a whole. An amount of 5 ppm to 0.5% by weight is preferred, a portion of 10 ppm to 0.1% by weight is particularly preferred, again in relation to the total mixture. Substances from the following groups can be considered:

• 1. reaction products of saturated or unsaturated aliphatic carboxylic acids with 3 to 30 C atoms and aliphatic oligoamines with 2 to 8 N atoms, which can additionally carry hydroxyl groups, or dialkanolamines or derivatives of such reaction products,
• 2. aliphatic sulfonium salts, which can be substituted by additional hydrophilic groups,
• 3. aliphatic or aromatic monocarboxylic acids and / or dicarboxylic acids with 3 to 16 carbon atoms or their water-soluble salts,
• 4. triazoles or derivatives thereof,
• 5. imidazoles or derivatives thereof,
• 6. thiazoles or derivatives thereof,
• 7. unsaturated aliphatic alcohols with 3 to 6 carbon atoms,
• 8. alkenylsuccinic acid, its water-soluble salts or derivatives of such alkenylsuccinic acids,
• 9. polymaleic acids or their water-soluble salts,
• 10. α-olefin-maleic anhydride copolymers,
• 11. Sulfamidocarboxylic acids or their water-soluble salts.

The substances of group f1) and their production are for example from EP-A C34 726, DE-A 31 09 826, DE-A 31 09 827, EP-A 103 737 and German patent application 195 20 269.4 known.

Examples of compounds of group f2) and methods for the manufacture thereof is described in JP-B 1972/10202, DE-A 18 06 653 and DE-A 22 08 894.

Group f3) inhibitors are mainly aliphatic Monocarboxylic acids with 5 to 12 carbon atoms and / or their sodium and potassium salts and aliphatic dicarboxylic acids with 4 to 12 C- Atoms and their mono- or disodium or potassium salts in Question. This group also includes aromatic ones Carboxylic acids such as benzoic, methylbenzoic, phthalic or Terephthalic acid and its sodium and potassium but also ammonium salts, which z. B. based on piperazine or morpholine.

Particularly suitable triazoles f4) are hydrocarbon triazoles, especially benzotriazole and toluotriazole.

Unsubstituted imidazole, alkyl- or aryl-substituted imidazoles such as 1- (C ₁ -C ₄ -alkyl) imidazoles or 1-phenylimidazole, aminoalkylimidazoles, z. B. N- (3-aminopropyl) imidazole, and quaternized imidazoles, e.g. B. with dimethyl sulfate quaternized N-vinylimidazole, the use of which as non-ferrous metal corrosion inhibitors is described in German patent application DE-A 196 05 509.

Particularly suitable thiazoles f6) are hydrocarbon thiazoles, z. B. benzothiazole.

A typical representative of an unsaturated alcohol f7) is Propargyl alcohol.

For alkenyl succinic acids f8) or their derivatives Ammonium salts of alkenylsuccinic acid halamides as described in the DE-A 41 03 262 are particularly emphasized. As Alkenyl radical is in particular a polyisobutyl radical from Interest.

Suitable polymaleic acids f9) are, for example, in EP-A 065 191 described.

Typical α-olefin-maleic acid copolymers f10) are in part or completely open to the dicarboxylic acid structures and are mostly derivatized with amines to amides or imides. As α-olefins come in particular those with 4 to 20 carbon atoms considered, e.g. B. isobutene, 1-octene or 1-dodecene.

Examples of sulfamidocarboxylic acids f11) are sulfonamides Anthranilic acid and neutralization products from Sulfamidocarboxylic acids with alkanolamines, dialkanolamines or trialkanolamines.

Of course, the corrosion inhibitors mentioned not only individually, but also in a mixture.

There are various configurations of the invention Procedure possible.

The coloring of the Textiles, for example, at 120-140 ° C in pressure vessels, which first at temperatures below 100 ° C pressure-free and therefore safe are open. On the other hand, the reductive post-cleaning of the Fabrics both in the dye liquor and in wash baths first above about 50 ° C with a satisfactory speed. The preferred temperature range during the aftertreatment is therefore at 50-100 ° C. The is particularly preferred Temperature range between 60 and 90 ° C, is particularly preferred Temperature range between 70 and 85 ° C.

The duration of the aftertreatment is usually 5-20 minutes, but can change under operational conditions deviating time period prove to be advantageous. The time period is from Parameters such as the temperature, the volume of the dye liquor or the wash bath and related the efficiency of the Addition of the aftertreatment agent, but of course also by affects the nature of the colorants used.

Another embodiment of the method according to the invention is a continuous process in which the textile materials be continuously passed through a cleaning bath.

To carry out the continuous variant of the The inventive method is the speed of goods, that is The speed at which the textile material moves through the fleet is carried out so that there is sufficient exposure time is guaranteed. That is generally at Goods speeds between 10 and 60 m / min the case. The fleet can do this have no flow or flow in cocurrent or countercurrent, based on the running direction of the textile material. Especially preferred is a method in which the liquor continuously in Counterflow to the textile material is supplied.

In a special configuration of the continuous variant the process of the invention is reductive post-cleaning preceded a washing step. This is particularly true in the reductive washing of prints on polyester or Textiles containing polyester are advantageous. Temperatures are advantageous here from 25 ° C to 60 ° C, preferably from 25 to 50 ° C and very particularly preferably from 30 to 45 ° C.

To carry out the method according to the invention, the Components a) b), c) and d) and the optionally added Component e) and other optionally added components locally and / or dose separately. However, one is preferred Embodiment in which a formulation is metered containing one or more compounds of the general formula Ia to I c, furthermore at least one buffer and at least one surfactant or at least one dispersant.

Another object of the present invention are Formulations containing one or more compounds of the general Formula Ia to c, furthermore at least one buffer and at least one surfactant or at least one dispersant. The Formulations according to the invention can be solid or liquid, liquid and in particular liquid aqueous are preferred Formulations. The formulations according to the invention can furthermore be granular still one or more of the above sulfonic acid compounds IIa or IIb contain, furthermore, the invention Formulations still one or more of the above Corrosion inhibitors included. With the help of the invention The process according to the invention is particularly simple in terms of formulations perform.

Usually you give per liter of the dye liquor or Wash bath volume 0.1 g to 5.0 g of the aftertreatment agent, based on the dry matter, too.

The process according to the invention can be colored or printed, polyester-containing textiles, especially reductive clean again. But you can, especially by using the Formulations according to the invention, polyester-containing textiles also very well rid of other impurities. In this case, the impurities that are foreign to the dye reductively decolorized.

Reserve printing applications are also possible, but not areas of the substrate to be colored with such mixtures or whose solutions are dealt with.

In the case of formulations containing dithionite, the formulations are carried out use according to the method, preferably in solid form. Here is however, the use of aqueous solutions is also possible.

When using dispersants and / or dispersants in liquid or dissolved state, this must be a solid Formulation according to the invention does not conflict with this. If the remaining components are in solid form, which at Sulfinic acid derivatives, acid binding substances, corrosion inhibitors usually the case is their binding capacity for the right Absorption of a liquid or dissolved component, especially in a share of 2 to 20% by weight of the total mixture, mostly for the provision of a granular and / or good pourable product.

The invention is illustrated by examples.

Examples and comparative examples

The following sulfinic acid derivatives were used for the examples and comparative examples:
Sulfinic acid 1 (S1): HO-CH ₂ -SO ₂ ^- Na ⁺
Sulfinic acid 2 (S2): N [-CH ₂ -SO ₂ ^- Na ⁺ ] _1.5 [-OH ₂ -SO ₃ ^- Na ⁺ ] _1.5

The dyes were dyed in an aqueous liquor under the following conditions:
Dyes 1-11 a / b / c% by weight (see Table 1)
Dispersant 1 1 wt .-%, based on the weight of the goods
Leveling agent 1% by weight, based on the weight of the goods
Fleet ratio 20: 1
pH 4.5 with acetic acid / sodium acetate buffer
Starting temperature 70 ° C
Heating rate 2 ° C / min
Dyeing temperature 130 ° C
Dyeing time 90 min
no subsequent cleaning.

The dispersant 1 used is a naphthalenesulfonic acid-formaldehyde condensation product with an average molecular weight M _w 6500 g / mol. Palegal®SFD, commercially available from BASF Aktiengesellschaft, was used as the leveling agent.

Stripes of textured polyester fabric each measuring 3.12 cm were used as textiles. After dyeing was complete, the dye liquor was allowed to cool to 80 ° C. Table 2 Coloring Examples 1-11: Coloring of the textiles

Comparative examples V 1.1 to V 1.11: reductive post-cleaning

The dyes were mixed with the sulfinic acids S1 and S2 pH value of 5 as in WO 98/03725, page 19, line 32 ff. described, or with sodium dithionite / NaOH (pH value: 12.5) cleaned. The post-cleaning effect was assessed then using a wash test according to DIN EN ISO 105-C03.

The parameters for post-cleaning were as follows:
Liquor ratio 1:20, duration 15 minutes, temperature 80 ° C,
Concentration: 8 g / l S1 or S2 or Na ₂ S ₂ O ₄ (sodium dithionite) technically from ACROS Organics

The concentration is to be understood as a g / l liquor including polyester fabric. Table 3 Comparative tests: post-cleaning without the addition of dispersants or surfactants

It can be seen from Table 2 that some dyes in Standard process of reductive post-cleaning under acidic conditions cannot be removed sufficiently.

4. Preparation of formulations according to the invention

First, formulations according to the invention were prepared Table 3 by simply mixing the listed Components and dilute with 15 ml of water each.

In the tables mean:
Dispersant 1: naphthalenesulfonic acid-formaldehyde condensation product with M _w 6500 g / mol.
Dispersant 2: naphthalenesulfonic acid-formaldehyde condensation product with M _w 8000 g / mol.
Dispersant 3 is a dispersant of formula III with M = Na, a = 0, b on average 25-30, d = 1.
Dispersant 4 is ethoxylated β-naphthol with an average of 12 ethylene oxide units.
Surfactant 1: with an average of 10 ethylene oxide units ethoxylated oleylamine.
Surfactant 2: polyvinyl pyrrolidone with an average M _w approx. 38000 g / mol.
Surfactant 3: C ₁₅ fatty alcohol, ethoxylated with an average of 5 ethylene oxide units
Surfactant 4: C ₁₆ -tet alcohol, ethoxylated with an average of 45 ethylene oxide units
Surfactant 5: castor oil, ethoxylated with an average of 30 ethylene oxide units
Surfactant 6: C ₁₃ alcohol, ethoxylated with an average of 5 ethylene oxide units, technical quality.

Table 4 continued

4. Examples of reductive post-cleaning in the presence of Surfactants and dispersants, general working instructions

After the dyeing step had ended, the dye liquor, cooled to 80 ° C. and containing the dyed polyester, was mixed with formulations according to the invention and kept at 80 ° C. for 15 minutes. The dye liquor was then drained off and the dyed polyester was rinsed with cold water for 5 minutes and dried. 4.1 Post-cleaning of the dyed polyester from dyeing example 9c

4.2. Post-cleaning of the dyed polyester from dyeing example 7

4.3. Colorings with dye mixtures

Example 1 was modified as follows: instead of a textured one Polyester fabric became a triacetate-polyamide mixed fiber fabric with a mixture of Disperse Orange 31, 0.2% Disperse Red 82, 0.3% by weight, and Disperse Blau 153 (0.6% by weight), colored. The mixture was then cooled to 60 ° C.

The dye liquor, cooled to 60 ° C. and in which the dyed polyester was located, was then mixed with formulations according to the invention and kept at 60 ° C. for 20 minutes. The dye liquor was then drained off and the dyed triacetate / polyamide mixed fiber fabric was rinsed for 5 minutes with cold water and finally dried.

It was found that the reductive post-cleaning in the presence of dispersants and surfactants in the acidic range also Fiber blends that are otherwise difficult to clean up, has clear advantages.

4.4 Soiling tests with multifiber strips

Fleets used for this test and the results are shown in Table 5. The soiling test was carried out in the following way:
For each test, 100 g of a liquor with the composition listed below were placed in a dyeing bomb and then 5 g of a multifiber fabric of the type ISO Multifiber Adjacent Fabric Type DW, commercially available from TESTEX G. Lauhaus, Bad Münstereifel, were added. The dyeing was then carried out at 60 ° C. for 30 minutes. The stain was then washed with cold water. The soiling behavior was assessed in particular on polyester.

The concentrations are to be understood as g or ml per 1 liquor.

The evaluation is based on the following scale:
++ no soiling
+ very little soiling
0 little dirt
- heavy soiling

4.5 Continuous acidic post-cleaning of polyester fabric

The continuous acidic post-cleaning was carried out on a continuous working system with seven washing compartments. Each wash compartment had a liquor content of 50 l each. The chemicals listed in the following table were used in the individual washing compartments. A total of 80 m of a 30 cm wide polyester fabric which had been pre-dyed over the entire area with 0.3 g of DY 198, 0.6 g of DR 92 and 0.6 g of DB 87 according to the recipes given above was continuously removed with an average residence time of 2 min cleaned per wash compartment. No chemicals were subsequently added during the term. Table 6

In the subsequent wash test based on DIN EN ISO 105-C03 wash fastnesses of 4-5 were achieved. Fastness to rubbing dry or wet (based on DIN EN 54021 105-X12) was also included 4-5.

4.6 Continuous pressure washing under acidic conditions

The continuous pressure washing was carried out on the same system as the continuous washing of dyeings. However, a fixed, unpurified print of disperse dyes on polyester was used as a pattern. The three printing pastes used had the following composition:

The recipe for the continuous post-washing of this print had the following recipes in the wash baths:

In the subsequent wash test based on DIN EN ISO 105-C03 wash fastnesses of 4 were achieved. Fastness to rubbing dry or wet (based on DIN EN 54021 105-X12) was 4-5.

Claims (8)

1. Process for the reductive post-cleaning of textile materials under acidic conditions, characterized in that a) one or more sulfinic acids of the general formulas I a to I c,

R ⁴ O (CR ¹ R ² ) _m SO ₂ MI a

N (R ³ ) _3-p [(CR ¹ R ² ) _m SO ₂ M] _p I b

N (R ³ ) _3-qr [(CR ¹ R ² ) _m SO ₂ M] _q [(CR ¹ R ² ) _n SO ₃ M] _r I c

in which the variables are defined as follows
R ¹ , R ² , R ^{4 are} identical or different and are independently hydrogen,
C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl,
R ^{3 are the} same or different and are selected independently
Hydrogen,
C ₁ -C ₁₈ alkyl,
C ₃ -C ₁₂ cycloalkyl, unsubstituted or substituted by one to three C ₁ -C ₄ alkyl radicals,
M the same or different and selected from equivalents of
Ammonium ions, alkali metal ions, alkaline earth metal ions;
m, n 1 or 2
p 1, 2 or 3
q 1 or 2; where if q = 1, r = 2; and in the event that
q = 2, r = 1 is selected.
where p is 2 when m is 0;
and wherein in formula I a at least one of the radicals R ¹ , R ² , R ^{4 is} a C ₁ -C ₆ alkyl, and still a) at least one buffer and b) at least one surfactant or c) at least one dispersant starts. 2. The method according to claim 1, characterized in that compounds I a or I b are selected from the compounds H ₂ NCH ₂ SO ₂ Na, HN (CH ₂ SO ₂ Na) ₂ , N (CH ₂ SO ₂ Na) ₃ , HIGH (CH ₃ ) SO ₂ Na, H ₂ NCH (CH ₃ ) SO ₂ Na, HN (CH (CH ₃ ) SO ₂ Na) ₂ , N (CH (CH ₃ ) SO ₂ Na) and sodium salts of 1- , 2-, 3-, 4- or 5-ethylhexylaminomethanesulfonic acid and -ethanesulfonic acid. 3. The method according to claim 1 or 2, characterized in that the pH is from 3.9 to below 5. 4. The method according to any one of claims 1 to 3, characterized in that one uses a dispersant selected from partially neutralized sulfated oxyalkylated phenols of the general formulas III and IV




or their mixtures, in which the variables are defined as follows:
a is between 0 and 180, preferably between 0 and 125
b is between 20 and 180, in particular between 35 and 125, where b ≥ a;
M is an alkali metal,
d is 0 or 1. 5. The method according to any one of claims 1 to 3, characterized characterized in that a dispersant is used, selected from Compounds available by sulfonation aromatic compounds such as naphthalene or naphthalene containing mixtures of aromatic compounds and then condensing the naphthalenesulfonic acids formed or arylsulfonic acids with formaldehyde. 6. The method according to any one of claims 1 to 5, characterized in that a) sulfonates of the formula II a or II b

R ⁴ O (CR ¹ R ² ) _m SO ₃ M II a

N (R ³ ) _3-p [(CR ¹ R ² ) _m SO ₃ M] _p II b

adds, where R ¹ , R ² , R ³ , R ⁴ , M, p and m have the same general meaning as in formulas I a to I c, the selection of these variables in individual cases for the compounds of formulas I a to I c and II a and II b need not be the same. 7. Solid or liquid formulation containing one or several sulfinic acids of the formula I a to I c, at least one Surfactant, at least one buffer and at least one Dispersant, and optionally at least one corrosion inhibitor and optionally at least one sulfonic acid of the general Formula II a or II b. 8. Use of formulations according to claim 7 for reductive Cleaning of textiles containing polyester.