Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • 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
  • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
  • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
• • 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
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
  • D06M15/03—Polysaccharides or derivatives thereof

Definitions

• the invention relates to compositions for the treatment of textile fiber material, a method for producing the composition and the use thereof for finishing textile material.
• the pretreatment of textile fiber material is used to remove unwanted accompanying substances.
• Cellulose substrates in particular contain a number of classes of compounds which can otherwise impair subsequent finishing steps.
• Surfactant formulations are used to remove fats in washing processes and complexing agents and dispersants are added to the treatment bath to remove unwanted hardness and heavy metals. If complexing agent mixtures are already acid-buffered formulations, their effect can be optimized by improving the solubility of alkaline earth or heavy metal salts in acid.
• Biodegradable phosphonates and polyacrylates are used today as effective complexing agents and dispersants, especially in commercially available formulations.
• EP 0 589 978 B1 describes alkyl polyglycosides as auxiliaries in textile pretreatment.
• the alkyl polyglycosides have a very high chemical and temperature resistance, which is a mandatory requirement in pretreatment processes such as alkaline boiling, desizing, acid demineralization and bleaching.
• Examples 2 and 3 describe adding commercially available phosphonates to the processes of alkaline boiling and bleaching in order to achieve a stabilizing effect of the peroxide and a dispersing effect of the hardness formers.
• the disadvantage of such a procedure is the use of two products and the use of non-biodegradable phosphonates and polyacrylates.
• DE 43 44 357 A2 describes a liquid washing and cleaning agent which, in addition to nonionic surfactants, especially alkyl polyglycosides, contains a dirt-removing polymer and organic builders, such as citric acid and water-soluble organic polymers such as in DE 42 21 381 C1. This mixture is used as a detergent and cleaning agent.
• WO 93/13256 describes the use of lipases for removing hydrophobic fatty acid esters from textiles.
• DE 43 12 010 A1 describes an enzymatic detergent which contains lipases, amylases, proteases and cellulases as enzymatic components. It also contains up to 10% by weight of anionic, nonionic, cationic and / or amphoteric surfactant and up to 40% of inorganic or organic builders.
• anionic, nonionic, cationic and / or amphoteric surfactant up to 40% of inorganic or organic builders.
• For peroxide stabilization in a bleaching stage e.g. B. sodium silicate or other organic stabilizers used.
• Enzyme components are known to support and improve washing processes.
• EP 0 441 197 A2 describes graft polymers of saccharides, partially neutralized maleic acid and the respective saccharide being introduced as monomer components and a pH of 4 being established when acrylic acid is added. In the case of a product, at least partial biodegradation was concluded.
• the products described as according to the invention are said to be suitable as additives for detergents and cleaning agents.
• copolymers containing sulfonic acid groups are only inadequately eliminated in sewage treatment plants due to their solubilizing sulfonic acid group in conjunction with their low molecular weight mean, which is evident from studies according to OECD 302 B.
• EP 0 289 895 B1 already succeeded in producing readily biodegradable sugar acrylic acid polymers, in which saccharides capable of enolate formation are polymerized in an alkaline solution with unsaturated carboxylic acids.
• the Use of this class of substances is described as a complexing agent and co-builder in washing and cleaning agents.
• DE 43 44 029 A1 describes special copolymers with saccharides capable of enolate formation, their mixtures described in EP 0 289 895 B1 with other complexing agents and their textile applications.
• Water glass is an inexpensive and COD-free hydrogen peroxide stabilizer and alkali buffer. In use, however, alkaline earth ions can result in deposits on textile goods and machine parts that cannot be removed even with mineral acids.
• Mixtures of water glass with complexing agents are described in EP 0 585 038 A1, the phosphonic acids, aminocarboxylic acids and polyacrylic acids contained therein not being based on renewable raw materials and not being biodegradable.
• the described polyacrylic acid Alcosperse® 175 can only be mixed during storage in a narrow SiO 2 / Na 2 O weight ratio (GVZ: weight ratio number).
• compositions in particular for the treatment of textile fiber material, containing glucose-free polymers of acrylic acid and saccharides which contain glucose as a raw material or reaction product.
• glucose-free comprises low-glucose polymers with a glucose content of less than 1% by weight, based on the polymer.
• the mixtures according to the invention ensure that at least 1 part by weight of one or more of the abovementioned additives is optionally present in the presence of water (ad 100% by weight).
• the compositions preferably contain 20 to 80 parts by weight of water, based on 80 to 20 parts by weight of the polymers or the mixtures of polymer and additive.
• mixtures according to the invention also have the advantage that they can be diluted with water and, as a result, mixtures with lower viscosity and thus better pumpability can be prepared.
• biodegradable dispersing complexing agents can be supported synergistically by adding further biodegradable complexing agents, such as sodium gluconate.
• biodegradable complexing agents such as sodium gluconate.
• table 3 and examples H and I it can be seen that sodium gluconate, whether produced directly in the product after polymerization or simply added when the product is mixed, supports the effect of a mixture of water glass and reference example 2.
• the polymers according to the invention and known per se, despite their polyelectrolyte character, are well suited for formulation with surfactants and do not tend to instability in mixing even at low pH values. Furthermore, it has surprisingly been found that these blends are outstandingly suitable for the treatment of fiber material in the most diverse process stages of textile finishing, in particular pretreatment.
• the polymers from acrylic acid and enolizable monosaccharides, oligosaccharides and / or polysaccharides in the alkaline pH range from 7 to 10. These polymers are expressly described in EP 0 289 895 B1.
• saccharides capable of enolate formation do not necessarily have to be raw materials can be used directly. These can also be produced from oligosaccharides or polysaccharides by means of acidic, alkaline or enzymatic processes before or during a polymerization.
• the combination according to the invention of alkyl polyglycosides with a sugar polymer in accordance with EP 0 289 895 B1 has the advantage that the properties of the surfactant, wetting and penetration of the textiles with liquor and removal of sizing, preparations and accompanying substances of all kinds, with the properties of a polyacrylate, dispersion of the hardness agents and the particle dirt, to combine positively and to receive an environmentally friendly and biodegradable textile auxiliary.
• the enzymes are preferably selected from amylases, catalases, cellulases, lipases, pectinases, proteases and / or glucose oxidases.
• compositions according to the invention especially for use, require a more or less large amount of water. This depends in particular on the intended use of the compositions.
• the selection of the low molecular weight organic and inorganic acids is not subject to any particular restriction. Accordingly, it is particularly preferred to select the low molecular weight organic acids from low molecular weight mono- or polycarboxylic acids, in particular citric acid, tartaric acid, lactic acid, gluconic acid and / or glucoheptonic acid.
• Phosphonic acids within the meaning of the present invention which are preferably used as additives preferably selected from HEDP, ATMP, DTPMP and / or HDTMP.
• the inorganic acids are preferably selected from mineral acids, in particular hydrochloric acid and sulfuric acid and also amidosulfonic acid.
• compositions for treating textile fiber material usually contain surfactant-containing constituents.
• surfactant-containing constituents For the purposes of the present invention, particular preference is given to anionic surfactants, nonionic surfactants and / or alkyl polyglycosides.
• the anionic surfactants are preferably selected from linear or branched C 8 -C 20 alkane sulfonates, alkane sulfates, alkane carboxylates or alkane ether carboxylic acids as well as alkyl benzene sulfonates and soaps (maximum 20% by weight).
• Nonionic surfactants in the sense of the present invention are selected in particular from linear or branched C 8 -C 20 fatty alcohol alkoxylates.
• a further embodiment of the present invention consists in a process for the preparation of the glucose-free compositions defined above, the polymers of acrylic acid and saccharides which contain glucose as a raw material or reaction product being treated with glucose oxidase. In this way, a glucose-free or low-glucose product is obtained which can be used particularly advantageously.
• the individual components are mixed according to a method known per se in the prior art.
• compositions according to the invention can be used by processes known per se for finishing textile material.
• Special Methods of textile finishing include the binding of polyvalent metal ions, the inhibition of water hardness, the dispersion of pigments as well as the use in washing, bleaching and dyeing liquors, especially for the aftertreatment of dyeings in textile materials.
• a mixture of 154 g of acrylic acid, 108.9 g of sucrose, 54.5 g of sodium methallyl sulfonate and water was partially neutralized with 39.6 g of 50% sodium hydroxide solution in the reactor, cooled to 25 ° C. and with 8.8 g of mercaptoethanol, 0.02 g of iron sulfate in 10.0 g of water and 3 g of 35% hydrogen peroxide. If the temperature rising in the reactor as a result of the onset of the polymerization reaction had risen above 75 ° C., the mixture was cooled back to 75 ° C. after the maximum temperature had been reached. If the temperature remained below 75 ° C., the temperature was raised to 75 ° C. after reaching the maximum temperature.
• the polymer was colored brown and clear. As stated, it had a viscosity of 40 mPas. 4% free glucose and 4% free fructose were formed. The determination of the total elimination, which resulted from biodegradation and elimination through adsorption, generally gave values of less than 40% in several measurement series according to OECD 302 B.
• Acrylic acid was added within 2 hours, and hydrogen peroxide was metered in for 30 minutes longer. The mixture was then stirred at 90 ° C for 30 minutes.
• the polymer had a viscosity of 400 mPas and contained 1.2% free glucose.
• compositions for textile finishing were compiled analogously to the above regulations, the composition of which can be seen in the table below.
• the information in Table 1 below represents percentages by weight.
• Table 1 Examples 2nd 3rd 4th 5 6 7 Polymer according to reference example 2 15 15 15 Polymer according to example 1 30th 4th 10th Gluconic acid; 50% 10th 10th 10th 10th Citric acid * H 2 O 5 5 5 5 Sulfuric acid conc.
• compositions for textile finishing were compiled analogously to the above regulations, the composition of which can be found in the table below.
• the SiO 2 / Na 2 O weight ratio in Table 2 was set by dissolving solid sodium hydroxide in 38 ° Bé water glass (GVZ 3.3), but can also be done by mixing with commercially available water glasses with a lower GVZ.
• Example A 1 Acid demineralization - discontinuous process
• Raw cotton fabric was treated for 30 minutes at 70 ° C. and a liquor ratio of 1:10 with a liquor which contained 5 g / l of the mixture according to Example 4. After the treatment, the fabric was washed warm and cold.
• the result was a textile material that was very well demineralized and could be used for all further treatments.
• the total hardness on the goods was reduced by 60%, the iron content by 50%, treatment with 5 g / l of the polymer according to Reference Example 1 or Reference Example 2 alone reduced the total hardness by only 30% and the iron content by 20% or 30, respectively %.
• Example A 2 Acid demineralization - discontinuous process
• Raw cotton fabric was treated as in Example A1 for 30 minutes at 70 ° C. and a liquor ratio of 1:10 with a liquor which contained 5 g / l of the mixture according to Example 4. 6 g / l sodium hydroxide solution 50%, 8 ml / l hydrogen peroxide 35% and 0.8 g / l of a high-affinity optical brightener (trade name "Tuboblanc® VA fl.”) Were then added without rinsing the liquor. Then it was rinsed hot and cold.
• a high-affinity optical brightener trade name "Tuboblanc® VA fl.
• the product reached a basic white of 81 and a fluorescence of 72 Berger units.
• Example B Acid demineralization - continuous process
• a liquor containing 6 g / l of the mixture according to Example 2 and 4 g / l of a wetting agent (trade name "Subitol DM”) was padded onto raw cotton knitwear.
• the liquor absorption was 100%
• the liquor temperature was 60 ° C
• the residence time was 30 minutes
• the residence temperature was also 60 ° C.
• the textile material was well demineralized and could be subjected to further treatment steps.
• the total hardness on the goods was reduced by 50% and the iron content by 40%, which was not achievable with less acidic complexing agents alone.
• a raw cotton fabric was impregnated with the following fleet: 0.2 g / l Epsom salt, 7 ml / l of the combination product mentioned in Example 5, 30 g / l sodium hydroxide 50%, 10 ml / l water glass 38 ° Bé, 40 ml / l hydrogen peroxide 35%.
• the fleet intake was 100%.
• the goods were then left at room temperature for 24 hours using the KKV method, then washed, rinsed and dried.
• the basic white rose from 18 to 82 Berger units.
• the same recipe with a 10 ml / l mixture according to Example 9 instead of 38 Bé water glass gave 83. Even without 7 ml / l product according to Example 5, 81 Berger units were still achieved here.
• a test according to Example D without water glass showed only 75 Berger units.
• a raw cotton fabric with a basic white of 18 Berger units was impregnated with the following fleet: 0.2 g / l Epsom salt, 2 or 6 ml / l of the product mentioned in Table 3 below, 20 g / l sodium hydroxide 50%, 40 ml / l hydrogen peroxide 35%.
• the fleet intake was 100%.
• the goods were then steamed at 102 ° C. for 30 minutes using the pad steam method, washed, rinsed and dried.
• Example E Discontinuous pre-cleaning and washing
• a raw cotton fabric was treated with a liquor which contained 3 g / l of the combination product according to Example 7 and 1 g / l of soda.
• the liquor ratio was 1:10, the temperature was 95 ° C. and the washing time was 30 minutes. It was then washed out hot and cold.
• a raw cotton fabric was treated with a liquor which contained 3 g / l of the combination product according to Example 7 and 3 g / l of soda.
• the liquor ratio was 1:20, the temperature 90 ° C and the washing time 30 minutes. It was then washed out hot and cold. The accompanying substances were completely removed and the properties of the textile corresponded to the standard of a washing process.
• Reference Example 1 showed no stain-removing effect and the fabric pattern remained hydrophobic.
• Example F2 Washing process with standardized cotton EMPA dirt fabric
• the test fabric was treated with a liquor containing 2 g / l of the combination product according to Example 7 and 1 g / l of soda.
• the liquor ratio was 1:40, the temperature was 60 ° C. and the washing time was 30 minutes. It was then washed out hot and cold. The whiteness rose from 19 to 31 Berger units. If instead of the product according to Example 7, the product according to Reference Example 2, or a pure nonionic surfactant, isotridecyl alcohol 6-fold ethoxylated, only 22 or 26 Berger units resulted.
• Raw cotton fabric was boiled at a liquor ratio of 1:10 in the presence of 5 g / l of the combination product according to Example 7 and 20 g / l NaOH 100% at 98 ° C. for 30 minutes.
• the whiteness of the goods rose from 22 to 39 Berger units.
• Example I Testing for alkaline earth dispersion in the presence of iron ions
• Example 5 The test was carried out as in Example H, but an additional 25 ° dH calcium ions (from calcium chloride) and 10 ° dH magnesium ions (from magnesium sulfate) were added to the test solution. Residue-free filters received a grade 1, coarse-grained residues as when using water glass without a dispersant received a grade 6. Table 5 product grade Water glass GV 3.3 6 Water glass GV 1.6 6 Example 9 3rd Example 10 2nd Example 11 2nd Comparative Example 3 6 Comparative Example 4 5

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Detergent Compositions (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

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Citations (5)

• 1996
  • 1996-04-13 DE DE19614628A patent/DE19614628A1/de not_active Ceased
• 1997
  • 1997-02-28 DE DE59712878T patent/DE59712878D1/de not_active Expired - Lifetime
  • 1997-02-28 AT AT97103334T patent/ATE371764T1/de not_active IP Right Cessation
  • 1997-02-28 EP EP97103334A patent/EP0801165B1/fr not_active Expired - Lifetime

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