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
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/02—After-treatment
  • D06P5/04—After-treatment with organic compounds
  • D06P5/08—After-treatment with organic compounds macromolecular
• • 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
• • 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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3715—Polyesters or polycarbonates

Definitions

• the present invention relates to a method for preventing or minimizing color position on fabric during a decoloring process, especially during a "stone-wash" process.
• the fabric is preferably indigo-dyed cotton or cotton-containing fabrics.
• the anti-color redeposition agent used is a polyester, preferably a terephthalic acid polyester-polyether polymer.
• the pumice stone was discovered to accelerate the aging process of the indigo-dyed parts.
• the "stone-wash look” is made possible by the fact that the dye is essentially only applied to the outer regions of the fibers. This is characteristic of an indigo dye. This is referred to as a so-called coat color, in which the color does not penetrate into the yarn, but it envelops like a coat and the core of the yarn or the fibers is not discolored.
• the enzyme used here is usually a cellulase.
• the cellulase is temporarily bound to the cellulose by an anchor and cleaves it to its 1,4-betaglucosidic linkage.
• the cellulase is temporarily bound to the cellulose by an anchor and cleaves it to its 1,4-betaglucosidic linkage.
• the cellulase is temporarily bound to the cellulose by an anchor and cleaves it to its 1,4-betaglucosidic linkage.
• the cellulase is temporarily bound to the cellulose by an anchor and cleaves it to its 1,4-betaglucosidic linkage.
• the surface of the cotton fiber on which the indigo dye is located partially detached.
• underneath, not colored and thus white areas of the cotton fiber come to light.
• the use of the cellulases achieves an optical effect, which corresponds to the use of pumice.
• the cellulases used in the enzymatic stone-wash process can be divided into two groups: acidic and neutral cellulases.
• the terms “acidic” and “neutral” are used to describe the pH at which the enzyme develops its optimum performance. For acid cellulases, this is the range of about 4 to 6, while neutral cellulases show their optimum performance at pH values of about 6 to 8.
• a major difference is the higher abrasion that allows acidic cellulases compared to neutral ones.
• acidic cellulases the same abrasion properties can be set when using 10 to 20% of the amount of neutral cellulase.
• acid cellulases allow shorter treatment times and are also significantly cheaper, which leads to an overall economic advantage. Disadvantages, however, are the so-called "backstaining" (color printing position).
• Under color printing position refers to a back discoloration or mulch including the cotton with peeled dye or dye on fiber remains. These deposits can be observed at various points, such as inside pockets, labels, seams, zippers, but also in particular on the inner and outer surface of the denim. Backstaining creates an undesirable low-contrast appearance of the product.
• the color printing position is a function of the cellulase mixture used, the dye, the type of surfactant used, the surfactant concentration and the pH.
• nonionic fatty alcohol ethoxylates with anionic alkanesulfonate to achieve an anti-redepositon effect is described.
• anionic surfactants lead to a negative interaction with the cellulase, such that their abrasiveness is reduced.
• the WO 01/57173 describes an enzymatic 2-component system by means of which it is possible to produce a good stone-wash effect on dyed cotton or cotton-containing fabrics with a simultaneously very low Backstaining.
• the 2-component system contains, in addition to a cellulase component, special aqueous polymer dispersions whose solid particles are styrene / (meth) acrylic acid ester copolymers which have been grafted onto starch as the graft base.
• the WO 95/35363 describes a method for producing a stone-wash effect by using acidic cellulases in the presence of color anti redeposition agents selected from the group of natural and synthetic, inorganic silicates, polyalkylene oxides, acrylic acid polymers and natural and synthetic or semisynthetic polysaccharides.
• color transfer inhibitors described in the prior art such as polyvinylpyrollidones, polyvinylpyridine N-oxides, etc.
• these compounds are not effective enough when it comes to backstaining
• indigo which may be - without wishing to be bound by theory - may be due to the extreme hydrophobicity of this dye.
• Polyesters are already preparable by reacting polymeric waste terephthalates, such as polyethylene terephthalate, polybutylene terephthalate or poly (cyclohexanedimethanol) terephthalate, glycols and oxyalkylated polyols having at least 3 hydroxyl groups, which are used in dyeing and Entfärbereaen to prevent the color printing position.
• polymeric waste terephthalates such as polyethylene terephthalate, polybutylene terephthalate or poly (cyclohexanedimethanol) terephthalate
• glycols and oxyalkylated polyols having at least 3 hydroxyl groups which are used in dyeing and Entfetzbeskeleton.
• the actually disclosed polyesters are further prepared using trimellitic acid and / or isophthalic acid or their derivatives.
• the object of the present invention is to provide a means which efficiently prevents the color printing position on textile fabric during a decoloring process, in particular during a stonewashing process.
• the agent should act as an anti-redeposition agent for the released dye, in particular indigo, or the dye-coated particles, such that it not only compared to the pure denim, but also with respect to typical accessories of denim or jeans such as pocket lining, stitching , Labels and zippers, which are often not made of cotton.
• soil release polymers soil release polymers
• these are preferably amphiphilic, preferably nonionic polyester-containing polyether monomer sequences.
• Polyetherols are used to prepare the polyether monomer sequences.
• Polyetherols in the context of the invention are compounds having one or 2 hydroxyl groups having at least 6 oxygen atoms, preferably at least 10 oxygen atoms and in particular more than 16 oxygen atoms.
• Diols in the context of the invention are compounds which have 2 hydroxyl groups and at most one, preferably no ether groups.
• the above data in mol% are conclusive and each independently and refer to the sum of components (A) to (D).
• the polyester is made using essentially no other component, i. less than 5 mol%, preferably less than 1 mol% of further components.
• the indication "at room temperature” stands for temperatures of 15 to 25 ° C, in particular 20 ° C.
• Compounds within the meaning of the main claim of the present invention are organic compounds which, in addition to carbon, hydrogen and oxygen after reaction, i. Incorporation into the polymer, i.d.R. have no further atoms.
• the dicarboxylic acid compounds, after incorporation into the polyester may carry not only carboxyl groups, but also carbonyl or hydroxyl groups, but e.g. have no sulfonyl or halogen groups.
• the dicarboxylic acid compound (A) are aliphatic and / or aromatic dicarboxylic acids and derivatives thereof, ie, for example, their monoesters, diesters, anhydrides or mixtures.
• the dicarboxylic acid compounds have - based on the dicarboxylic acid or dicarboxylic acid group - preferably 3 to 40 carbon atoms.
• aromatic dicarboxylic acid compounds may in particular be terephthalic acid, isophthalic acid, phthalic acid, their mono- and dialkyl esters with C 1 -C 5 -alcohols, such as, for example, dimethyl terephthalate, mixtures of these also being mentioned Connections are possible.
• aliphatic dicarboxylic acid compounds are malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid dialkyl esters.
• isophthalic acid and phthalic acid in particular terephthalic acid, and also their dimethyl, diethyl, dipropyl and dibutyl esters.
• the dicarboxylic acid used in the process according to the invention is terephthalic acid, preferably greater than 90 mol%, preferably greater than 95 mol%, based on the di- or tricarboxylic acid compounds used.
• other dicarboxylic acid compounds may also be used.
• Aromatic dicarboxylic acids in addition to terephthalic acid, in particular isophthalic acid, phthalic acid, their mono- and dialkyl esters with C1 to C5 alcohols, such as. Dimethyl terephthalate, of course, mixtures of these components are possible.
• aliphatic dicarboxylic acid equivalents are malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid dialkyl esters.
• terephthalic acid and phthalic acid and their dimethyl, diethyl, dipropyl and dibutyl esters.
• tricarboxylic acid compounds whereby highly branched polymer structures become accessible.
• Suitable for this purpose are e.g. Trimellitic acid or its derivatives such as anhydrides and esters. However, their use is usually to be avoided.
• the polyol compounds (D) preferably have 3 to 12 carbon atoms.
• Examples of the polyol compounds having at least 3 OH groups are: pentaerythritol, trimethylolethane, trimethylolpropane, 1,2,3-hexanetriol, sorbitol, mannitol, mono-, di- and triglycerol, 1,2,3- Butanetriol, 1,2,4-butanetriol. Preference is given to the use of glycerol.
• polyetherols (C) are adducts of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof with water or aliphatic C 1 - to C 18 -, preferably C 1 - to C 6 -, alcohols such as methanol, ethanol, propanol or butanol. Preference is given to addition products of ethylene oxide over methanol or water.
• polyetherols which preferably represent more than 30% by weight of a major portion of the polymer.
• examples of these are polyethylene glycol, polypropylene glycol, polybutylene glycol and addition products of ethylene oxide, propylene oxide, butylene oxide or their mixtures of aliphatic alcohols such as methanol, ethanol, propanol, butanol or long-chain fatty alcohols.
• Preference is given to polyethylene glycols having weight average molecular weights of 500 to 10,000 g / mol, and polyethylene glycol monomethyl ethers having molecular weights of 2,000 to 5,000 g / mol.
• the diol compound (B) for example, ethylene glycol, 1,2- or 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 3-methoxy-1,2-propylene glycol and their dimers and trimers can be used in the present invention.
• the diol compound (B) preferably has 2 to 6 carbon atoms. In principle, mixtures of different diols are possible. Preference is given to the use of ethylene glycol and / or propylene glycol.
• polymers anionically can e.g. by condensation of anionic monomers, e.g. Sulfophthaloyl, Sulfoisophthaloyl- and Sulfoterephthaloyl- groups which are used in the form of their salts, in particular as alkali metal or ammonium salts.
• anionic monomers e.g. Sulfophthaloyl, Sulfoisophthaloyl- and Sulfoterephthaloyl- groups which are used in the form of their salts, in particular as alkali metal or ammonium salts.
• aliphatic anionic monomers derived from sulfonated aliphatic diesters e.g. Derive maleic acid, adipic acid, sebacic acid, etc.
• nonionic PET polyethylene terephthalate
• PET polyoxyethylene terephthalate
• polyesters polyethylene glycols
• polyethylene glycols are preferred with molecular weights of 2,000 to 10,000 g / mol.
• the recovered PET-POET copolymers are solid at room temperature and have weight average molecular weights of 5,000 to 40,000 g / mol.
• liquid at room temperature polyester-polyether copolymers represented by the formula X- (OCH 2 -CH 2 ) n - [- (OOC-R 1 -COO-R 2 ) u -] - OOC-R 1 -COO- (CH 2 -CH 2 O) n -X wherein each R 1 radical is a 1,4-phenylene radical, optionally mono- or di-C 1 -C 3 -alkyl-substituted; the R 2 radicals are essentially ethylene radicals, 1,2-propylene radicals or mixtures thereof; each X is independently hydrogen, a C1 to C12 hydrocarbon radical, especially ethyl or methyl; each n is independently from 7 to 115 and u is from 3 to 10.
• polyesters are the subject of WO 99/09125 , which is hereby incorporated by reference for the further definition of the polyesters, there called amphiphilic polymers, as the subject of the disclosure of this application.
• the synthesis of the polymers used according to the invention can be carried out in the form of a direct reaction of all monomer building blocks in one step, so that statistically distributed polymers (so-called "random" structures) are obtained.
• Another mode of preparation is a multi-step synthesis e.g. in such a way that a precondensation of different components takes place.
• temperatures of about 80 to 350 ° C and pressures of normal pressure to ⁇ 1 mbar are set.
• the condensation is carried out in the temperature range of 150 to 280 ° C in the presence of the usual polycondensation and transesterification catalysts.
• the polymers obtained can be adjusted to different molecular weights. These are preferably between 1,000 and 40,000 g / mol.
• Suitable catalysts are known from the literature compounds. If the free dicarboxylic acids or anhydrides are used as the component, p-toluenesulfonic acid is the preferred catalyst. If dicarboxylic acid dialkyl ester is used as the component, the usual transesterification catalysts are used, such as, for example, mixtures of calcium acetate and antimony oxide, organic and inorganic tin and zinc compounds (eg stannanes, zinc acetate or the TEGO® catalysts of Degussa) or tetraalkoxytitanates, such as titanium tetraisobutanolate or tetraisopropoxide.
• the usual transesterification catalysts are used, such as, for example, mixtures of calcium acetate and antimony oxide, organic and inorganic tin and zinc compounds (eg stannanes, zinc acetate or the TEGO® catalysts of Degussa) or tetraalkoxytitanates,
• the condensation can be carried out in the presence of antioxidants, e.g. substituted phenols such as 2,5-di-tert-butylphenol, 2-methylcyclohexyl-4,6-dimethylphenol, phosphorous acid or other antioxidants commonly used therefor.
• antioxidants e.g. substituted phenols such as 2,5-di-tert-butylphenol, 2-methylcyclohexyl-4,6-dimethylphenol, phosphorous acid or other antioxidants commonly used therefor.
• a common aftertreatment is, for example, a bleaching with hydrogen peroxide, which leads to a clear color lightening.
• the polymers used in the process according to the invention can be obtained both in solid and in pasty to liquid form.
• the additives are also preferred in solid form. It is possible, depending on the morphology, to use the polymers both as 100% form e.g. milled form or in supported form i. by applying the polymer to a solid support by means of the granulation methods described in the prior art.
• these compounds can also be used in the form of a matrix.
• matrix here is the blend of amphiphilic polyester-polyether copolymers with, for example, nonionic surfactants, such as alcohol ethoxylates, alcohol propoxylates, mixed alcohol alkoxylates, alkyl polyglucosides, glucose amides, polyethylene glycols, polypropylene glycols, mixed polyalkylene glycols, solvents such as isopropanol, propylene glycol, glycol ethers, water, etc.
• nonionic surfactants such as alcohol ethoxylates, alcohol propoxylates, mixed alcohol alkoxylates, alkyl polyglucosides, glucose amides, polyethylene glycols, polypropylene glycols, mixed polyalkylene glycols, solvents such as isopropanol, propylene glycol, glycol ethers, water, etc.
• polyester-polyether copolymers may also be supported on support materials, e.g. Zeolites, phosphates, citrates, sodium sulphate, pumice or pumice equivalents such as perlites, etc. and thereby e.g. be converted into free-flowing powdery compounds.
• support materials e.g. Zeolites, phosphates, citrates, sodium sulphate, pumice or pumice equivalents such as perlites, etc. and thereby e.g. be converted into free-flowing powdery compounds.
• Such compounds can be advantageously incorporated in powdered stone wash formulations.
• the antiredepositol agents used in the process according to the invention are preferably used in amounts of from 0.1 to 20% by weight, based on the Stone Wash formulation (excluding abrasives).
• formulations are based on a combination of mechanical treatment and enzyme treatment (stone-washing and biostoning). Instead of pumice sintered perlites are often used, which lead due to their hardness to less abrasion during the process. In addition, they are smaller than pumice stones, have a larger surface area, which makes it possible to rinse the stones with the wash liquor.
• the central building block of the enzymatic formulations for producing a stone-wash effect is one or more cellulases. Essentially, two groups of cellulases are used: acid and neutral.
• these formulations contain further constituents.
• a buffer system which has the task of keeping the pH constant within certain limits in order to ensure optimal performance of the enzyme system.
• the buffering of the cellulase bath is very important, since alkalinity is often introduced by the tissue in particular.
• surfactants Another essential ingredient of these formulations are surfactants. Their task is u.a. to accomplish rapid wetting of the cellulosic fiber such that the cellulase can attack the fiber as quickly as possible. Further functions of the surfactants are the removal of excess sizing agent, the suspension of the indigo dye and the emulsification of oil and fat components. In addition, they continue to serve as dispersants and Lauffaltenverhinderer within this application.
• Nonionic surfactants such as the fatty alcohol alkoxylates described in the prior art, castor oil ethoxylates etc. are preferred.
• the reason for the preferred use of nonionic surfactants lies in their good wetting of the fibers with at the same time little influence on the cellulase activity.
• Anionic surfactants can sometimes have negative effects on the enzymes, such that their activity is reduced or incompatibilities occur.
• the proportion of surfactant within the formulations is preferably in the range from 5 to 25% by weight (excluding abrasives).
• Stone-Wash formulations may also contain other ingredients, e.g. Enzyme activators, solubilizers, solvents, antioxidants, builders or sequestering agents.
• Enzyme activators e.g. Enzyme activators, solubilizers, solvents, antioxidants, builders or sequestering agents.
• Examples of typical solvents are: ethylene glycol, propylene glycol, and their oligomers / polymers, terpenes, hydrocarbons, etc.
• Examples of enzyme activators are: proteins, salts of monosaccharides, e.g. Mannose and xylose.
• Typical solubilizers are: short-chain alcohols, benzenesulfonate salts, propylene glycol, benzoates, etc.
• Builders or sequestrants are often used: organic phosphates, phosphonates, polyacrylic acids, polyvinyl alcohols, polyvinylpyrollidones, borates, citrates, etc.
• the process of producing denim or denim consists essentially of three main steps: desizing, abrasion (stoning / biostoning) and bleaching.
• the sizing agent which is usually starch
• this step was accomplished by alkaline scrubbing at higher temperatures.
• amylases or combinations of amylases and lipases These break down the starch polymers into short, water-soluble fragments that can be washed out.
• the background of this step is the creation of soft denim surfaces, prevention of banding and preparation of the fabric for the subsequent step of abrasion.
• surfactants are also used in this step.
• one or more rinsing steps can take place before the next treatment step.
• the abrasion step is the described stone-washing or biostoning or combinations of stone-washing and biostoning.
• cellulose fragments are removed from the surface, creating the classic stone-wash look.
• the cellulases After achieving the required abrasion, the cellulases must be deactivated to stop further degradation of the tissue. This is done in a subsequent washing process, at alkaline pH values and higher temperatures at which the enzyme denatures. Finally, the tissue i.d.R. under standard conditions bleached with the bleaching agents described in the prior art, e.g. Hypochlorite.
• the antiredeposition agents described in the method according to the invention are also distinguished, inter alia, by their affinities for hydrophobic surfaces such as, for example, polyester, polyamide or their blended fabrics with cotton. Since the accessories of jeans such as pocket lining, zippers, labels, seams, etc. are often made of these materials, it is recommended additives of the invention not only in the actual stone-wash process but before, ie in the desizing of the fiber. Here, these accessories receive an efficient surface impregnation, which essentially means that the indigo released in the stone-wash process is less attracted to these surfaces.
• a total of 640 g (1.45 mol) of polyethylene glycol monomethyl ether having a weight-average molecular weight of about 440 g / mol (MARLIPAL 1) were introduced into a 2 l multi-necked flask with glass stirrer, heating bath, inert gas inlet, distillation head, packed column, distillation bridge, vacuum distributor, distillation flask, cold trap and internal thermometer / 12 from Sasol Germany GmbH), 388 g (2.0 mol) of dimethyl terephthalate, 110.5 g (1.2 mol) of glycerol, 145.8 g (1.4 mol) of neopentyl glycol, 1.0 g of 2,6- Di-tert-butyl-p-cresol (Ionol from Shell) and 1 ml of tetraisopropyl orthotitanate submitted under inert gas.
• MARLIPAL 1 polyethylene glycol monomethyl ether having a weight-average molecular weight of about
• reaction mixture was slowly heated to temperatures of 150 to 220 ° C and collected the methanol formed. After most of the theoretically expected amount of methanol was collected, the reaction mixture was cooled, the column removed, vacuum applied and the mixture heated again up to a maximum of 230 ° C. The unreacted in the reaction diol / polyol mixture was collected as distillate.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Textile Engineering (AREA)
• Polyesters Or Polycarbonates (AREA)
• Detergent Compositions (AREA)
• Coloring (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

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• 2003
  • 2003-12-10 DE DE10358097A patent/DE10358097A1/de not_active Ceased
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