Classifications

• • 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
  • D06L4/15—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
  • D06L4/12—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 for whitening dyed textiles and the textiles produced therewith.
• the classic denim, or denim is a weave of indigo ring-dyed warp yarn and mostly undyed weft yarn.
• the ring coloration of the warp yarn is the reason for the typical signs of wear that give the jeans their individual appearance in the course of their lives.
• the only superficially adhering to the yarn dye (usually indigo alone or in combination with sulfur black) is gradually removed by mechanical abrasion during washing and use and the white fiber core emerges increasingly. This is increasingly the case, especially in exposed areas such as seams and wearing folds. Since there is a great need on the part of the consumer to purchase garments with utility optics as new, the provision of the so-called used or vintage look is now one of the most commercially important fashion effects in the leisure sector.
• hypochlorites for example sodium hypochlorite.
• hypochlorites for example sodium hypochlorite.
• hypochlorites for example sodium hypochlorite.
• chlorine bleach an easily available, inexpensive and efficient bleaching agent is available, with which a large number of dyes, including indigo or indigoid dyes, can be decolorized oxidatively.
• this approach has the disadvantage that large amounts of (adsorbable organically bound halogens) AOX-polluted wastewater incurred, which often have to be post-treated to comply with regulatory limits.
• Chlorine bleach is very toxic to aquatic organisms. Therefore, the use of chlorine-based chemicals in environmental and consumer organizations is highly criticized.
• hypochlorites is also possible for local lightening, for example by spraying. In practice, however, this method is usually not used due to the strong corrosion and etching effects as well as the poor controllability of the bleaching effect.
• potassium permanganate For the partial bleaching of denim articles in the spray process, the use of potassium permanganate is state of the art.
• serious disadvantages have come to light here as well in the meantime.
• potassium permanganate exhibits high toxicity to aquatic organisms and its massive use leads to high levels of heavy metals in wastewater.
• Chemical Prohibition Ordinance ChemVerV
• the release of potassium permanganate in Germany requires a proof of use in order to prevent misuse for explosives or drugs. Similar restrictions exist in many other countries, making the purchase of potassium permanganate laborious and making stockholding more difficult.
• an additional process step to remove the resulting manganese dioxide is also necessary in the spray treatment.
• hypochlorite and potassium permanganate As alternatives for hypochlorite and potassium permanganate a number of approaches have been proposed, but also have serious disadvantages and could not prevail in practice.
• vat dyes can be converted into the soluble leuco form by reducing agents, removed from the fiber, and the textile so lightened.
• sugars such as glucose
• these processes have the disadvantage of working at high temperatures (> 80 ° C.) and high alkalinity (pH> 11) must become.
• large amounts of wastewater accumulate, which also have an increased biological and chemical oxygen demand due to the high organic load. This problem also occurs analogously when using other reducing agents such as keto compounds, for example hydroxyacetone.
• reducing processes for producing local bleaching effects are fundamentally unsuitable since, as in a closed washing drum, an overall reducing environment can not be produced and thus the locally produced leukoform is rapidly reoxidized by atmospheric oxygen.
• US 3,384,596 C discloses the use of peroxycarboxylic acids such as monoperoxophthalic acid and m-chloro-peroxobenzoic acid in the presence of alkaline earth salts as a bleaching agent at alkaline pH.
• US 4,443,352 C proposes the use of monoperoxophthalic acid and its water-soluble salts as a bleach-enhancing component of a powdered detergent formulation. The method called stain bleaching in household washing at alkaline pH.
• 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 spot bleaching in household laundry at 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 complex and not economically feasible in practice, because the iron salt must be applied in an upstream treatment step and removed in a subsequent treatment step using large amounts of complexing agents again. To achieve good effects, a longer treatment time at temperatures of 70 ° C and higher is also necessary, which makes 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 are subject to the same restrictions as the oxidizing agent according to the ChemVerV, such as permanganate and therefore are not suitable as an alternative under this aspect.
• peroxodisulfate solutions are as well as Fenton solutions are not suitable for achieving local effects by spray or brush application.
• EP 0 176 124 A2 (AT 44 763 E) relates to the use of a suspension in water containing as bleach component a peroxycarboxylic acid derived from a dicarboxylic acid having 8 to 13 carbon atoms as a castable bleach.
• DT 26 20 723 AI relates to bleaching or cleaning agents, in particular with a bleaching effect at low temperatures.
• the object of the present invention is therefore to provide a method for whitening dyed textiles, which on the one hand makes it possible to lighten the textile flatly or uniformly in the desired shade, but on the other hand also locally limited, for example, by spraying or brush application in freely selectable intensity to bleach.
• the process should provide comparable results in its lightening effect as using chlorine-based bleach or potassium permanganate, while significantly reducing potential environmental hazards and dangers. In particular, no environmentally hazardous chemicals should be used and an entry of AOX or heavy metals into the wastewater should be excluded.
• organic peroxycarboxylic acids in particular certain linear or cyclic aliphatic or aromatic peroxocarboxylic acids or dicarboxylic acids containing hydrophobic side groups, preferably alkyl radicals having at least 5 carbon atoms, particularly preferably having 5 to 30 carbon atoms and more preferably having chain lengths of 6 to 10 C-atoms, have a very high whitening effect on dyed textiles.
• indigo and indigoid dyes can be bleached under moderate conditions, so that a local treatment, for example by spraying, can be carried out simply and practically.
• hydrophobic usually refers to the association of non-polar groups or molecules of an aqueous environment. This characterizes substances that do not mix with water and usually “roll off” on surfaces.
• Non-polar substances such as fats, waxes, alcohols with long alkyl radicals - ie with the exception of methanol, ethanol and propanol - alkanes, alkenes etc. are hydrophobic. Dissolution of hydrophobic substances in water generally results in a so-called hydrophobic effect, and in some small, hydrophobic species, such as methane or xenon, even entropically unfavorable clathrate structures are formed. Therefore, the solubility of these substances in water is generally low. Hydrophobic substances are almost always lipophilic, meaning they dissolve well in fat and oil. Surfaces having a contact angle greater than 90 ° to water are also referred to as hydrophobic. Hydrophobic radicals in the context of the present invention thus include, in particular, a contiguous radical of at least 5 carbon atoms, a carbon chain, which are preferably saturated with hydrogen atoms to form an alkyl radical or an aryl radical.
• Particularly preferred bleaching agents according to the invention are aromatic peroxycarboxylic acids consisting of one or more fused aromatic rings, optionally substituted by one or more other peroxycarboxylic acid groups at any position.
• aromatic peroxycarboxylic acids of the invention may be further substituted with at least one functional group selected from alkyl, aryl, carboxylate, sulfonate, halide, nitro or hydroxy groups at any point on the aromatic ring system.
• Preferred examples are: mono- or diperoxo-ortho, -meta or -para-phthalic acid, mono- or diperoxo-4-methyl-o-phthalic acid, mono- or diperoxo-l, 8-naphthoic acid.
• the peroxycarboxylic acids may be used both in the acid form and as salts or may also be generated in situ by the addition of activated carboxylic acid derivatives (for example as anhydrides) and a hydrogen peroxide source or otherwise in the process.
• the salts used are preferably alkali metal or alkaline earth metal salts, for example Li, Na, K, Mg or Ca salts.
• the treatment can be carried out particularly efficiently under acidic pH conditions, although it is known to the person skilled in the art that peroxycarboxylic acids, for example peracetic acid, at a pH close to the pKa value, ie in the neutral to weakly alkaline , the highest Have bleaching efficiency.
• the pH of the solution is in the range of 0 to 7, more preferably in the range of pHl to pH5, most preferably in the range of pHl, 5 to pH3.5.
• Native and synthetic thickeners salts such as alkali and alkaline earth sulfates, phosphates and, if required, marking dyes, for example dyes, wetting agents, humectants such as glycerol, urea or dispersants or further auxiliaries, are added as further additives to the application liquor.
• marking dyes for example dyes, wetting agents, humectants such as glycerol, urea or dispersants or further auxiliaries.
• the pH of the solution is particularly preferably adjusted with mineral acids or organic acids.
• very particularly preferred in this sense are low-volatile acids, that is, acids having a vapor pressure ⁇ 20 Pa at 20 ° C, such as citric acid, maleic acid, lactic acid, phthalic acid, phosphoric acid, sulfuric acid or hydrogen sulfates.
• the colored substances are brought into contact with a solution containing all or part of the peroxycarboxylic acid or its salts by means of a spraying, dipping or brushing process.
• a wide variety of textiles or textile fabrics can be brought into contact with the peroxycarboxylic acids.
• these dyes are selected 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, as well as with combinations of these dyes.
• Another embodiment of the present invention includes bleached fabrics obtainable by a method as defined above. Jeans, as defined by these bleached fabrics, are particularly preferred.
• the bleaching effect was determined on two different denim products each with determination of the Y values according to CIE with Datacolor International SF 600 plus CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65.
• a standard KMnO solution has been achieved, particularly preferably> 60%, very particularly preferably> 80%.
• Reference example 1 Reference example 1:
• denim 1 non-desized, scraping pretreatment with sandpaper
• denim 2 desized, stonewash treatment
• a rectangular area of 120 cm 2 was marked and covered with adhesive film at the edges against the adjacent areas. These areas were uniformly sprayed with 2 g each of an aqueous solution of 20 g / l potassium permanganate (0.38 normal) and the fabric samples were then weighed to control the amount applied.
• the fabric samples were neutralized in a washer-extractor together with untreated denim fabric as ballast first 10 min at 50 ° C and a liquor ratio of 1: 8 with 4 g / l sodium bisulfite, then 3 times cold rinsed at a liquor ratio of 1:10 and then dried in a tumbler.
• the y-value according to CIE Datacolor International SF 600 Plus-CT, Aperture 30 mm LAV, 4-fold measurement, standard light calibration D 65 was measured on each of the samples thus obtained on and off the spray-treated area Degree of lightening determined by ⁇ .
• MPMS monoperoxomaleic acid
• MMPP magnesium bis-monoperoxophthalate hexahydrate
• MPPS monoperoxophthalic acid
• MPDCS monoperoxycis-cyclohexane-1,2-dicarboxylic acid
• Monoperoxo-4-methyl-phthalic acid Mg salt (MPMP) was prepared analogously to Comparative Example 1 as a normal aqueous solution containing 18.4% by weight of MPMP, 2.5% by weight of sodium sulfate, 0.4% by weight of xanthan thickener and additionally 1 g / l of a marking dye is applied in the same amount on both standard denim products.
• the marking dye was removed in the subsequent rinsing steps and only served to make the spray history and the uniformity of the job more visible.
• the preparation and measurement were carried out in the same manner as in Comparative Example 1.
• MMPP magnesium bis-monoperoxophthalate hexahydrate
• Standard Denimware 2 was treated on a spin-on machine at a liquor ratio of 1: 8 with a liquor containing 15 ml / 1 Na hypochlorite solution (120 g / l active chlorine) for 15 min at 50 ° C. Then it was rinsed twice with cold soft water at a liquor ratio of 1:10 and then in 2 steps first with 4 g / l sodium bisulfite and then with 4 ml / 1 hydrogen peroxide 35% each for 10 min at a liquor ratio of 1:10 and a temperature of 40 ° C neutralized. After drying in the tumbler, the Y-value was determined according to CIE (Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65).
• CIE Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65.
• Standard Denimware 2 was adjusted to a pH of 3.0, 20 on a washer-spinner at a liquor ratio of 1: 8 with a liquor containing 20 g / L magnesium bis-monoperoxophthalate hexahydrate (MMPP) and adjusted with citric acid min treated at 60 ° C. The mixture was then rinsed twice with soft water at 40 ° C. at a liquor ratio of 1:10. After drying in the tumbler, the Y-value was determined according to CIE (Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, 4-fold measurement, calibration standard light D 65).
• CIE Datacolor International SF 600 Plus-CT, aperture 30 mm LAV, 4-fold measurement, calibration 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
  • 2015-04-15 PE PE2016001996A patent/PE20161487A1/es unknown
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  • 2015-04-15 US US15/305,938 patent/US20170051452A1/en not_active Abandoned
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