Classifications

• • D06L3/025—
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
• • 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
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/13—Fugitive dyeing or stripping dyes
  • D06P5/132—Fugitive dyeing or stripping dyes with oxidants

Definitions

• the invention relates to a process brightening dyed textiles, and to textiles produced thereby.
• the classical jeans fabric is a fabric consisting of a warp yarn ring-dyed with indigo and a mostly undyed weft yarn.
• the ring-dyeing of the warp yarn is the reason for the typical wear phenomena that provide the jeans with its individual appearance in the course of its useful life.
• the dye usually indigo alone or in combination with sulfur black, which adheres to the yarn only superficially, is gradually removed by mechanical abrasion during laundering and use, and the white fiber core becomes increasingly apparent. Especially on exposed parts, such as seam bulges and wrinkles, this is even more apparent.
• these areas are selectively sprayed with a bleaching solution that destroys the dye more or less, depending on the desired intensity of the brightening effect. This produces a perfect illusion of traces of usage and having been worn on a new denim article.
• hypochlorites for example, sodium hypochlorite.
• Sodium hypochlorite is a readily available, cost-effective and efficient bleaching agent by which a large number of dyes, including indigo or indigoid dyes, can be oxidatively decolorized.
• this procedure has the disadvantage that large amounts of waste water loaded with adsorbable organic halogens (AOX) are obtained, which often need to be aftertreated to meet the limits prescribed by the authorities.
• AOX adsorbable organic halogens
• Sodium hypochlorite is very toxic to aquatic organisms. Therefore, the use of chlorine-based chemicals is heavily criticized by environmental and consumer organizations.
• hypochlorites is also possible for local brightening, for example, by spraying.
• this method is usually not applied in practice because of the strong corrosion and caustic effects as well as the fact that the bleaching effect is difficult to control.
• vat dyes especially indigo
• indigo can be converted to the soluble leuco form by reducing agents, removed from the fiber, and thus the textile can be brightened.
• sugars such as glucose
• EP 0 654 557 A the use of sugars, such as glucose
• these methods have the disadvantage of having to be operated at high temperatures (>80° C.) and at a high alkalinity (pH >11). Further, large amounts of waste water are obtained, which in addition have an increased biological and chemical oxygen demand because of the high organic load.
• reducing methods are basically unsuitable for producing local bleaching effects, because, unlike in a closed washing drum, an environment having an overall reducing effect cannot be created, and thus the locally produced leuco form is quickly reoxidized by atmospheric oxygen.
• U.S. Pat. No. 3,384,596 C discloses the use of peroxocarboxylic acids, such as monoperoxophthalic acid and m-chloroperoxobenzoic acid, in the presence of alkaline earth metal salts as bleaching agents at an alkaline pH.
• U.S. Pat. No. 4,443,352 C proposes the use of monoperoxophthalic acid and its water-soluble salts as a bleach-enhancing component of a powdery detergent formulation.
• a process stain bleaching in household laundry at an alkaline pH is mentioned.
• An analogous use of monoperoxophthalic acid magnesium salt is claimed in EP 0 027 693 A.
• DE 34 00 950 A discloses the use of monoperoxophthalic acid magnesium salt in combination with an alkali bromide and sulfonamides in a detergent formulation, also for stain bleaching in household laundry at an alkaline pH.
• WO 95/25195 A proposes the use of a hydrogen peroxide source in combination with an iron salt at a strongly acidic pH for bleaching indigo-dyed textiles.
• This combination has long been known as Fenton's reagent.
• Fenton's reagent the process is very complicated and cannot be performed in an economically efficient way in practice, because the iron salt must be provided in a preliminary treatment step, and must be removed again in a downstream treatment step using large amounts of complexing agents.
• an extended treatment time at temperatures of 70° C. and higher is necessary, making this process very energy-intensive.
• WO 95/20643 A proposes the use of peroxodisulfates as an oxygen source in combination with a transition metal catalyst.
• peroxodisulfates as oxidants are subject to the same limitations according to ChemVerV as permanganates, and therefore they are not suitable as alternatives under this aspect.
• peroxodisulfate solutions as well as Fenton's solution are not suitable for achieving local effects by spraying or paintbrush application.
• EP 0 176 124 A2 (AT 44 763 E) relates to the use of a suspension in water containing, as a bleaching component, a peroxocarboxylic acid derives from a dicarboxylic acid having from 8 to 13 carbons, as a pourable bleaching agent.
• DT 26 20 723 A1 relates to bleaching or cleaning agents, especially with a bleaching effect at low temperatures.
• DT 26 12 587 A1 relates to bleaching agent preparations containing a watersoluble aliphatic peroxy compound and a thickener.
• EP 0 160 342 A2 discloses liquid bleaching solutions containing aliphatic peroxy compounds as solid, particulate, essentially water-insoluble components.
• the object of the present invention to provide a process for brightening dyed textiles that enables the whole surface of the textile to be brightened uniformly in the desired shade on the one hand, but also to be bleached in a locally limited way, for example, by spraying or paintbrush application, in a freely selectable intensity.
• the process should enable results comparable to those obtained using chlorine-based bleaching agents or potassium permanganate, while significantly reducing possible disadvantages and dangers for the environment.
• no environmentally harmful chemicals should be used, and an emission of AOX or heavy metals into the waste water should be excluded.
• a process for brightening dyed textile fabrics characterized in that said fabrics are treated with an aqueous solution (liquor) containing an aliphatic or aromatic organic peroxocarboxylic acid with hydrophobic radical, especially alkyl radical or alkyl radical, consisting or at least 5 carbon atoms as an active component.
• aqueous solution containing an aliphatic or aromatic organic peroxocarboxylic acid with hydrophobic radical, especially alkyl radical or alkyl radical, consisting or at least 5 carbon atoms as an active component.
• organic peroxocarboxylic acids especially certain linear or cyclic aliphatic or aromatic peroxocarboxylic acids or -dicarboxylic acids, that contain hydrophobic pendant groups, preferably alkyl radicals with at least 5 carbon atoms, more preferably with 5 to 30 carbon atoms and even more preferably with chain lengths of from 6 to 10 carbon atoms, have a very high brightening effect on dyed textiles.
• hydrophobic pendant groups preferably alkyl radicals with at least 5 carbon atoms, more preferably with 5 to 30 carbon atoms and even more preferably with chain lengths of from 6 to 10 carbon atoms
• indigo and indigoid dyes can be bleached under moderate conditions, so that a local treatment, for example, by spraying, can be performed simply and under practicable conditions.
• hydrophobic usually designates the association of non-polar groups or molecules of an aqueous environment. It characterizes substances that do not mix with water and mostly let it “roll off” on surfaces.
• Non-polar materials such as fats, waxes, alcohols with long alkyl radicals, i.e., except for methanol, ethanol and propanol, alkanes, alkenes etc.
• hydrophobic materials are dissolved in water, there is generally a so-called hydrophobic effect, and with some small hydrophobic species, such as methane or xenon, even entropically unfavorable clathrate structures form. Therefore, the solubility of such materials in water is generally low.
• hydrophobic materials are almost always lipophilic, i.e., they dissolve well in fat and oil. Surfaces exhibiting a contact angle of more than 90° with water are also referred to as “hydrophobic”.
• hydrophobic radicals within the meaning of the present invention include, in particular, a contiguous radical of at least 5 carbon atoms, a carbon chain preferably saturated with hydrogen atoms to form an alkyl radical or aryl radical.
• aromatic peroxocarboxylic acids consisting of one or more condensed aromatic rings, optionally substituted with one or more further peroxocarboxylic acid groups at any possible position.
• aromatic peroxocarboxylic acids according to the invention may further be substituted with at least one functional group selected from alkyl, aryl, carboxylate, sulfonate, halide, nitro or hydroxy groups at any possible position in the aromatic ring system.
• mono- or diperoxo-ortho-, -meta- or -paraphthalic acid mono- or diperoxo-4-methyl-o-phthalic acid, mono- or diperoxo-1,8-naphthalic acid.
• the peroxocarboxylic acids may be employed both in the acid form and as salts, or also be produced in situ by the addition of activated carboxylic acid derivatives (for example, as anhydrides) and a hydrogen peroxide source, or in some other way in the process.
• activated carboxylic acid derivatives for example, as anhydrides
• hydrogen peroxide source for example, as anhydrides
• alkali or alkaline earth metal salts are preferably employed, for example, Li, Na, K, Mg or Ca salts.
• the treatment can be performed particularly efficiently under acidic pH conditions, although the skilled person knows that peroxocarboxylic acids, for example, peracetic acid, have the highest bleaching efficiency at a pH near the pKs values, i.e., in the neutral to weakly alkaline range.
• the pH of the solution is within a range of from 0 to 7, more preferably within a range of from pH 1 to pH 5, even more preferably within a range of from pH 1.5 to pH 3.5.
• native and synthetic thickening agents such as alkali and alkaline earth metal sulfates, phosphates and, if needed, marking dyes, for example, dyes, wetting agents, humectants, such as glycerol, urea, or dispersing agents or other auxiliary agents are added to the application liquor.
• marking dyes for example, dyes, wetting agents, humectants, such as glycerol, urea, or dispersing agents or other auxiliary agents are added to the application liquor.
• dyes serves for a better visual trackability of the course of spraying. This is particularly important to practice, because the purple permanganate strongly colors the spraying solution while the spraying solution according to the invention is basically colorless.
• pH ranges either occur by themselves because of the reactants employed, or may be adjusted by further additives. It is particularly preferred according to the present invention to adjust the pH of the solution with mineral acids or organic acids. Even more preferred in this respect are low volatile acids, i.e., acids having a vapor pressure of ⁇ 20 Pa at 20° C., such as citric acid, maleic acid, lactic acid, phthalic acid, phosphoric acid, sulfuric acid, or hydrogensulfates.
• acids having a vapor pressure of ⁇ 20 Pa at 20° C. such as citric acid, maleic acid, lactic acid, phthalic acid, phosphoric acid, sulfuric acid, or hydrogensulfates.
• a wide variety of methods for contacting the dyed fabrics with the peroxocarboxylic acid are available to those skilled in the art. It is particularly preferred in this respect to contact the dyed fabrics completely or partially with solutions containing peroxocarboxylic acid or salts thereof by a spraying, dipping or coating process.
• a wide variety of textiles or textile fabrics can be contacted with the peroxocarboxylic acids. It is particularly preferred in this respect to employ textile fabrics made from cellulose fibers or cellulose fibers in admixture with natural or synthetic fibers, dyed with various dyes. It is particularly preferred according to the present invention to select these dyes from the groups of vat, direct or sulfur dyes.
• the process of the present invention is particularly suitable for textile fabrics dyed with indigo, indigoid dyes or sulfur black, and with combinations of such dyes.
• Another embodiment of the present invention includes bleached textiles obtainable by a process as defined above. Jeans are particularly preferred within the meaning of the definition of such bleached textiles.
• peroxocarboxylic acids were employed in a concentration that corresponds to approximately three times the normality of a 2% potassium permanganate solution as employed on average today.
• the bleaching effect was determined on two different denim fabrics, each with determining the Y values according to CIE with Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, measurement in quadruplicate, calibration with standard light D 65.
• the Y value according to CIE was measured (Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, measurement in quadruplicate, calibration with standard light D 65) each on and beside the spray-treated area, and the degree of brightening was determined from the difference as ⁇ Y.
• MPMA monoperoxomaleic acid
• MMPP magnesium bis(monoperoxophthalate) hexahydrate
• MPPA monoperoxophthalic acid
• MPDCA monoperoxo-cis-cyclohexane-1,2-dicarboxylic acid
• MMPP magnesium bis(monoperoxophthalate) hexahydrate
• 1-normal aqueous solutions containing 25% by weight MMPP, 2.5% by weight sodium sulfate and 0.4% by weight xanthan gum thickener were prepared and adjusted to a pH of from 5.5 to 2.5 with phosphoric acid.
• 2.0 g was applied to standard denim fabric 2 in the same way as in Comparative Example 1, processed in the same way, and measured.
• Standard denim fabric 2 was treated on a washer-extractor at a liquor ratio of 1:8 with a liquor containing 15 ml/l Na hypochlorite solution (120 g/l active chlorine) at 50° C. for 15 min. This was followed by rinsing twice with cold soft water at a liquor ratio of 1:10, and subsequently, the fabric was neutralized in 2 steps at first with 4 g/l sodium bisulfite and then with 4 ml/l hydrogen peroxide 35% for 10 min each at a liquor ratio of 1:10 and a temperature of 40° C. After drying in a tumbler, the Y value according to CIE of one specimen was measured (Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, measurement in quadruplicate, calibration with standard light D 65).
• Standard denim fabric 2 was treated on a washer-extractor at a liquor ratio of 1:8 with a liquor containing 20 g/l magnesium bis(monoperoxophthalate) hexahydrate (MMPP) at 60° C. for 20 min after adjusting to pH 3.0 with citric acid. This was followed by rinsing twice with soft water at 40° C. at a liquor ratio of 1:10. After drying in a tumbler, the Y value according to CIE of one specimen was measured (Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, measurement in quadruplicate, calibration with standard light D 65).

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Coloring (AREA)
• Detergent Compositions (AREA)
• Treatment Of Fiber Materials (AREA)

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• 2014
  • 2014-04-24 DE DE102014207727.3A patent/DE102014207727A1/de not_active Withdrawn
• 2015
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  • 2015-04-15 US US15/305,938 patent/US20170051452A1/en not_active Abandoned
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