Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/673—Inorganic compounds
  • D06P1/67391—Salts or oxidising-compounds mixtures
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/647—Nitrogen-containing carboxylic acids or their salts
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/653—Nitrogen-free carboxylic acids or their salts
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/673—Inorganic compounds
  • D06P1/67333—Salts or hydroxides
  • D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/34—Material containing ester groups
  • D06P3/52—Polyesters
  • D06P3/54—Polyesters using dispersed dyestuffs
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/922—Polyester fiber

Definitions

• the invention relates to a process for dyeing polyester fibers having textile goods, in which the textile goods in an alkaline containing a disperse dye Dyebath treated at a temperature above 100 ° C. becomes.
• polyester dyeing process at temperatures above 100 ° C - i.e. under overpressure - allows shorter dyeing times than reach under normal pressure.
• HT High temperature
• HT conditions in the dyeing processes commonly used the following problem in the acid dye bath: While of the dyeing process are low molecular weight oligomers from the Fiber interior released when spinning continuous polyester fibers occur as by-products. These low molecular weight Oligomers accumulate in the acid dye bath Cooling of the dye liquor on the fiber surface and on the Surfaces of the dyeing devices. Through these deposits the technological properties of the textile goods, such as. Running and grip properties, significantly deteriorated.
• the dyeing devices are through the oligomer deposits are dirty. Furthermore, in particular with dark shades when using an acidic Dye baths require reductive or alkaline cleaning processes.
• alkaline dye baths Under alkaline conditions that is Solubility of the oligomers increased. Furthermore, one finds partial saponification of the released oligomers takes place, whereby the unwanted deposits significantly reduced become. Furthermore, alkaline dyeing can be used in many cases no reductive or alkaline aftertreatment become. When using the known acid dye baths the dyeing process is generally the only stage of treatment in acidic medium. By alkaline staining can accordingly avoid a pH change and thus the risk of imported alkali is minimized. Another advantage is that single-bath dyeing of polyester-cellulose fiber blends with direct dyes also become possible in alkaline, which additional Choices for appropriate direct dyes creates. It also becomes alkaline when used Dye bath basically possible, washing out or Desizing polyester fabrics in a bath with the dye to combine. The recrystallization continues of fiber degradation products from splitting and peeling processes prevented by the alkali.
• the disperse dyes used in the acid dye bath are sometimes unstable in the alkaline dye bath.
• the dyes are destroyed by hydrolysis of ester compounds in the side chains of the dye molecules.
• the degree of this hydrolysis depends to a large extent on the pH of the dye bath during the entire dyeing process.
• the pH is subject to fluctuations that can lead to non-reproducible dyeing results.
• Another problem is represented by heavy metal ions and multivalent metal ions in the dyebath, the presence of which in varying concentrations cannot be reliably excluded on an industrial scale.
• the influence of heavy metal and metal ions (eg Cu 2+ , Fe 2+ ) on the dyeing result is generally considerably greater in the alkaline dye bath than in the acid dye bath.
• the concentration of those dissolved in the dye bath Auxiliary substances limited by the fact that at too high a concentration the generally poorly soluble disperse dyes no longer in solution despite the use of dispersants can be held.
• the invention is accordingly based on the object a process for dyeing textile material made of polyester and whose fiber mixtures of the type mentioned at the beginning improve that the above problems avoided become.
• the deposition of oligomers is said to Dye material and dyeing devices avoided and at the same time a large-scale reproducible, consistently high quality Coloring result can be achieved.
• a dyeing aid can be created with which solves the above problems.
• This object is achieved according to one aspect of the invention in that the adjustment of the pH of the dye bath by initially adding a buffer mixture Glycine and / or a glycine derivative and an alkali before starting of the dyeing process, and that the dye bath Perborate salt is added.
• This solution creates a double buffer system, through which a sufficient pH constancy until the end guaranteed the dyeing process and at the same time reductive Processes is counteracted without the disperse dye through the buffer substances from the solution is ousted.
• the invention lies inter alia. based on the knowledge that at known alkaline dyeing process, the pH is not sufficient is kept stable. Especially through the saponification the initially set pH value of the oligomers by consumption of alkali towards the end of the dyeing process which has the consequence that initially saponified and dissolved Oligomers fail again. This effect is caused by a powerful buffer mixture counteracted. Furthermore are unwanted pH changes due to acidic or alkaline Dye bath components prevented by the buffer system and thus achieves a constant coloring result.
• a glycine / sodium hydroxide buffer (or glycine / glycine alkali metal salt buffer) is used for buffering, which works chemically as follows:
• That glycine and sodium hydroxide solution in the context of the invention as a buffer interact through which a pH consistency until the end of dyeing was achieved by experimental variation the ratio of glycine / sodium hydroxide solution.
• the coloring result was optimal when the components mentioned in one by the corresponding buffer equation the dye bath for the desired pH ratio were added. If the relationship in favor of Shifted alkali, i.e. produces a pH greater than 9.5, this shows an instability of the dyes, i.e. the Coloring is not reproducible. Will the relationship favor of the glycine is shifted, so is the buffer capacity no longer sufficient and the final pH is significantly below 9.0, which leads to a redeposition of the oligomers, or their Degradation products, leads.
• both glycine and a Glycine derivative in which a hydrogen of the amino group through an organic group is replaced.
• Unsubstituted Glycine is particularly beneficial because when using a glycine derivative the uptake another proton for acid formation is difficult the setting of the buffer equilibrium slows down.
• the Show hydrophobic residues of a substituted amine group also an increased dispersing effect, through which the disperse dye is kept longer in the dye bath and thus the dyeing process is extended.
• a perborate salt preferably sodium perborate
• a perborate salt is therefore additionally added to the dye bath in accordance with the invention such that hydrogen peroxide as the oxidizing agent and a pH-stabilizing mixture of borax and sodium hydroxide solution according to the following are used at the dyeing temperature Equation is released: 4NaBO 3 + 5H 2 O ⁇ 4H 2 O 2 + Na 2 B 4 O 7 + 2NaOH
• the sodium perborate fulfills a double function: on the one hand, borax and sodium hydroxide can stabilize the pH value of the dye bath in the desired dye range.
• the buffer capacity of the borax is based on hydrolytic cleavage to a low-water polyboric acid. In the following reaction scheme it becomes clear that an equilibrium is created in the presence of borax and sodium hydroxide solution. If sodium hydroxide solution is used to saponify oligomers, further borax can be split, ie the pH is maintained: Na 2 B 4 O 7 + (1 + x) H 2 O ⁇ 2 B 2 O 3 .xH 2 O + 2OH - + 2Na +
• sodium perborate releases H 2 O 2 at the dyeing temperature and thus acts as an oxidizing agent, counteracting reductive processes which can negatively influence the dyeing result in alkaline.
• dehalogenation of the dyes by heavy metals is counteracted under reductive conditions.
• Various other fiber accompanying substances can also have a dye-destroying reductive potential, which is counteracted by the hydrogen peroxide formed.
• the sodium perborate acts as a dye stabilizer.
• oxidation of the dyes as is desired in order to regress the color pigment, for example when dyeing cellulose fibers with vat dyes, is to be avoided within the scope of the invention.
• the usable concentration of sodium perborate is limited so that the dyeing result is not adversely affected by the undesirable oxidation of the dyes in this case.
• a buffer system based only on sodium perborate cannot have the required buffer capacity without the dyeing result being adversely affected by damage to the dyes. For this reason, two buffer systems are proposed according to the invention in order to achieve the required buffer capacity without negative effects on the dyes.
• the selected buffer systems together have a sufficient high capacity, are for the desired pH range (around pH 9.3) optimally suitable, ecologically harmless and applicable on an industrial scale.
• sodium chloride added to the buffer mixture becomes.
• the NaCl has no direct influence on the buffer effect. About the ion concentration in the dye bath to be kept as low as possible and the dye to precipitate out To avoid NaCl is preferably at most in one stoichiometric ratio to glycine added.
• NaCl is used in known dyeing processes so that the Dye from the dye liquor on the fiber by shifting of the solubility balance pulls or not resolves again in the fleet.
• concentrations used for this lie significantly above those in the context of the invention suggested NaCl concentrations.
• a sequestering agent with the essential constituents nitrilotriacetic acid and polycarboxylates is added to the dyebath.
• This combined sequestering agent binds multivalent metal ions and heavy metals as well as water hardness formers, which can negatively influence the dyeing result.
• the sequestering agent with the essential constituents nitrilotriacetic acid and polycarboxylates has proven to be particularly effective in the pH range from 9 to 10 without a negative influence on the dyes (for example demetallization) or a failure of the dyes to be noted.
• Nitrilotriacetic acid in the pH range of 9-12 of interest has a sequestering effect of approx. 200 mg / l for Ca 2+ , whereas the optimal sequestering effect of approx. 300 mg / l for Fe 3+ is at pH 1.5-3. This is compensated for by the use of a carboxylate with a sequestering effect of only approx. 60 mg / l for Ca 2+ at pH 8-10, but approx. 550 mg / l for Fe 3+ at pH 9-12.
• Nitrilotriacetic acid is therefore particularly suitable for Ca 2+ ions, whereas carboxylate is better suited for the sequestration of Fe 3+ ions.
• the sequestering agent is preferably used in connection with the above-mentioned buffer system, but can also lead to a considerable improvement in the dyeing result even when isolated.
• the initial pH can the dyeing process in the range of about 9.3 to 9.4 lie. The majority are available in this pH range Disperse dyes are still sufficiently stable.
• the final pH of the dyeing process is 9.0 not less. This is confirmed by a corresponding Buffer capacity reached. This way there will be a failure Oligomers already in solution at the end of the dyeing process reliably avoided because below pH 9.0 are the oligomers and their degradation products when falling Temperatures in the cooling process of the dye are no longer soluble.
• the concentration ratio of glycine to sodium hydroxide solution (33%) in the buffer mixture can preferably be about 1.9 or less.
• the amount of caustic soda should be adjusted that an initial pH of 9.3 to 9.4 is reached becomes.
• the amount of glycine determines the buffering capacity Compensation for alkali-consuming substances.
• the concentration ratio of glycine to sodium chloride is preferably about 1.3.
• a dyeing aid is proposed according to the invention, which glycine or a glycine derivative, a lye and contains a perborate salt.
• the lye - preferably Sodium hydroxide solution - can of course before the dyeing process can also be added separately.
• the dyeing process according to the invention is both for pure polyester fibers as well as for mixed fibers, e.g. Polyester / cellulose fiber blends suitable.
• the textile material is made using a standard high-temperature dyeing process dyed at approx. 130 ° C in a dyeing machine. Subsequently only a hot rinse is required. In order to becomes a reproducible coloring with technologically improved Textile produced.
• the acid coloring is carried out using 1 g / l Setamol WS (brand name Manufacturer BASF AG, Ludwigshafen) and pH 4.5 by adjustment with acetic acid.
• the colorimetric evaluation of the color difference is based on of the CIELAB values Delta C and Delta H are reproduced.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Coloring (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Applications Claiming Priority (2)

Publications (3)

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ID=7851942

Family Applications (1)

Country Status (6)

Cited By (1)

Families Citing this family (5)

Citations (4)

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• 1997
  • 1997-12-15 DE DE19755647A patent/DE19755647A1/de not_active Ceased
• 1998
  • 1998-11-24 AT AT98122283T patent/ATE328151T1/de not_active IP Right Cessation
  • 1998-11-24 EP EP98122283A patent/EP0924334B1/fr not_active Expired - Lifetime
  • 1998-11-24 DE DE59813571T patent/DE59813571D1/de not_active Expired - Lifetime
  • 1998-12-11 US US09/210,320 patent/US6004357A/en not_active Expired - Fee Related
  • 1998-12-14 JP JP10354476A patent/JPH11241279A/ja active Pending
  • 1998-12-14 BR BR9805442-2A patent/BR9805442A/pt not_active Application Discontinuation

Patent Citations (4)

Non-Patent Citations (1)

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