Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/364—Organic compounds containing phosphorus containing nitrogen
• • 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

Definitions

• the invention relates to aqueous solutions of phosphonic acids and / or their salts and in particular their use as complexing agents for the treatment of cellulosic fiber materials used in demineralization processes and used to stabilize bleaching solutions containing peroxide become.
• Complexing agents are used in the refinement of cellulosic fiber material, remove the interfering metal ions during a treatment or something mask that impairment of the process during treatment is reduced.
• complexing agents are also used, whereby in textile bleaching processes mainly DTPMP and in the bleaching of non-digested Wood pulp DTPA is used (ibid., P. 426-428).
• the described Use concentration is 0.1 - 0.2 wt .-%, based on the respective anhydrous complexing agent.
• amino carboxylic acids are assessed unfavorably. With the exception of the technically ineffective NTA, EDTA and DTPA are not biodegradable and are also not eliminated in sewage treatment plants by adsorption. Since all amino carboxylic acids are suspected of remobilizing toxic heavy metals - SCH ⁇ BERL and HUBER, Tenside Surfactants Detergents 25 2 (1988) 105-106 - they are checked in surface waters that are used for drinking water production. Maximum quantity restrictions for NTA in household detergents up to restrictive prohibitions of any use of EDTA or DTPA already apply today in textile finishing, wood and pulp industry depending on national and regional laws and regulations.
• Phosphonates which are better at the risk of remobilization of heavy metals be assessed, see GLEDHILL and FEIJTEL, The Handbook of Environmental Chemistry, Vol 3, Part F, pp. 261-285 (1992) are also considered not to be harmless classified because they are also not biodegradable and according to OECD 302B investigations can only be inadequately eliminated through adsoption.
• Phosphorus levels in wastewater whether it is a textile plant or a pulp mill, have strict limits may be subject to any improvement in this elimination data from great interest.
• the object of the invention is to provide aqueous solutions of phosphonic acids and / or to produce their salts which have an active substance content of at least 25% by weight, at least based on free phosphonic acid or the complexing agent Make liquids stable for 6 months at room temperature. Furthermore is the object of the invention to provide a new, effective and environmentally friendly process for demineralizing cellulose-containing Fiber material and for the stabilization of hydrogen peroxide Bleaching solutions for native textile fiber materials and kraft pulps.
• aqueous solutions of the phosphonic acid mentioned and / or their Salts with an active ingredient content of at least 30% by weight, in particular To produce 40 wt .-% with the desired storage stability.
• the mentioned partially neutralized or free phosphonic acids as complexing agents are used, it is special in the sense of the present invention preferred, this in an amount of 0.002 to 0.20 wt .-%, in particular in an amount of 0.005 to 0.05% by weight, based on the active substance To use acids and the dry amount of fiber.
• peroxide bleaches in the event that hydrogen peroxide used as peroxide use, preferably in an amount from 0.1 to 15% by weight, in particular from 0.2 to 5% by weight, based on the dry amount of fiber used.
• the bleach is particularly preferred at a pH in the range from 7 to 14, in particular in the range from 9 to 13.
• the temperature can in this case, for example, in the range from 20 to 140 ° C., in particular 70 to 120 ° C. can be set. If necessary, it is also possible to suspend the magnesium salts add, the amount of magnesium by up to 0.5 wt .-%, in particular 0.01 to 0.2 wt .-% is increased.
• Another embodiment of the present invention is its use of the above-mentioned aqueous solutions for demineralizing cellulosic fiber material, with aminophosphonic acids as complexing agents with at least 6 phosphonate groups.
• demineralization of cellulosic fiber material is also possible directly with the above-mentioned phosphonic acids of the general formula I and / or II use as a complexing agent.
• salts of To use phosphonic acid of the general formula I is to be understood as meaning that preferably at least one hydrogen atom of phosphonic acid is replaced by an alkali metal, alkaline earth metal, ammonium or amine ion.
• alkali metal alkaline earth metal
• ammonium or amine ion for the purposes of the present invention, they are particularly preferred the aqueous solutions around those of triethylenetetramine hexa (methylenephosphonic acid).
• phosphonic acids of the general formula I particularly preferred, mixtures of diethylenetriaminepenta (methylenephosphonic acid) and to use triethylenetetramine hexa (methylenephosphonic acid).
• the weight ratio of diethylenediaminepentamethylenephosphonic acid is particularly preferably to triethylenetetramine hexa (methylenephosphonic acid) 1 to 1 to 5 to 1.
• the final product contained 32% by weight of TTHMP. This value is usually based on the amine used related, since technical aminopolyphosphonates beginning with the ATMP consist of mixtures which, in addition to the highly phosphonomethylated and eponymous component also less phosphonomethylated Homologues and other by-products included.
• amines especially those that are technically available in large quantities, e.g. Tetraethylene pentamine, pentaethylene hexamine, but also polyethylene imines with weight averages up to 50000.
• Mathis-Labomat TM 100 ° C (internal temperature measurement), 90 min, 10% by weight consistency, 1.0% by weight NaOH, 1.5% by weight hydrogen peroxide.
• the complexing agents were each adjusted to 30% by weight of active substance, based on free acid.
• Table 3 shows that 0.05% by weight of TTHMP used as 30% by weight Active substance solution, even when reducing hydrogen peroxide 0.2% better whiteness than comparison tests without TTHMP.
• a non-pretreated cotton jersey was treated with a solution of 0.2 g / l Epsom salt, 40 ml / l hydrogen peroxide 35% by weight, 15 g / l sodium hydroxide 50% by weight, 5 g / l Felosan JET ® and 2 g / l TTHMP solution from Example 1 padded (90% by weight liquor pickup) and held for 20 hours at room temperature.
• the Berger whiteness rose from 15 to 68, the residual peroxide was 27% by weight. Without the addition of TTHMP, the whiteness was only 63 and the residual peroxide was 2% by weight.
• An untreated cotton jersey was made with a solution of 30 g / l sodium hydroxide solution 50% by weight, 2 g / l Cotoblanc® TAA and 4 g / l TTHMP solution from example 1 treated for 30 minutes at 98 ° C and a liquor ratio of 1:10. Calcium decreased from 530 to 270 ppm, magnesium from 220 to 130 ppm and iron from 38 to 26 ppm. The comparison test without adding TTHMP gave 480 ppm calcium, 190 ppm magnesium and 35 ppm iron.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Textile Engineering (AREA)
• Paper (AREA)
• Detergent Compositions (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)

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Citations (6)

• 1998
  • 1998-10-27 DE DE19849379A patent/DE19849379A1/de not_active Withdrawn
• 1999
  • 1999-10-26 DE DE59903638T patent/DE59903638D1/de not_active Expired - Lifetime
  • 1999-10-26 EP EP99121341A patent/EP0997523B1/fr not_active Expired - Lifetime
  • 1999-10-26 AT AT99121341T patent/ATE229065T1/de active
  • 1999-10-26 ES ES99121341T patent/ES2188086T3/es not_active Expired - Lifetime

Patent Citations (6)

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