EP1141471B1 - Procede pour produire des materiaux textiles contenant de la cellulose - Google Patents

Procede pour produire des materiaux textiles contenant de la cellulose Download PDF

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Publication number
EP1141471B1
EP1141471B1 EP99967949A EP99967949A EP1141471B1 EP 1141471 B1 EP1141471 B1 EP 1141471B1 EP 99967949 A EP99967949 A EP 99967949A EP 99967949 A EP99967949 A EP 99967949A EP 1141471 B1 EP1141471 B1 EP 1141471B1
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EP
European Patent Office
Prior art keywords
case
cellulosic
crosslinker
crosslinking catalyst
weight
Prior art date
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Expired - Lifetime
Application number
EP99967949A
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German (de)
English (en)
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EP1141471A1 (fr
Inventor
Manfred Blauth
Friedrich Reinert
Jürgen Reichert
Klaus Bergmann
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BASF SE
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BASF SE
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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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/419—Amides having nitrogen atoms of amide groups substituted by hydroxyalkyl or by etherified or esterified hydroxyalkyl groups
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/45—Shrinking resistance, anti-felting properties

Definitions

  • the present invention relates to an improved process for the production of cellulose-containing textile materials by treatment with a crosslinker based on N-methylol ethers in the presence of a magnesium chloride-based crosslinking catalyst.
  • non-iron textile materials can be obtained by the method according to the invention.
  • An essential part of the textile equipment of cellulose-containing textiles is the so-called high-grade finishing.
  • This web-like or knitted fabric is treated with crosslinking agents.
  • the crosslinkers are, for example, and 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone-2, also referred to as 1,3-dimethylol-4,5-dihydroxyethyleneurea ("DMDHEU"), and its derivatives with alcohols.
  • DMDHEU 1,3-dimethylol-4,5-dihydroxyethyleneurea
  • An essential component of a finishing recipe is a catalyst.
  • magnesium chloride or mixtures of magnesium chloride with Lewis or Bronsted acids are used.
  • Other catalysts such as zinc nitrate, zinc chloride or ammonium chloride are also common.
  • crosslinkers and catalysts usually come in the finishing of other aids such. Softener for use.
  • the most important standard process is the dry crosslinking process.
  • the textile material is impregnated with the finishing liquor containing the crosslinker (typical amount for pure cotton fabric: 40-45 g / l) and the crosslinking catalyst (typical amount: 12 g / l), and squeezed off, for example with a padder. It is then dried at higher temperatures and crosslinked ("condensed") either in the same working step or separately in a condensation apparatus. This works usually at condensation temperatures of 150 to 190 ° C.
  • the condensation time is usually 15 seconds to 4 minutes; the higher the condensation temperature, the shorter the condensation time.
  • wet crosslinking process In addition to the dry crosslinking process, the wet crosslinking process has recently gained in importance, because so far only textiles, especially cotton, with the highest quality of equipment, i. with very high smoothness after washing and very good wrinkle recovery with acceptable tear resistance, can be produced.
  • wet crosslinking process is a mineral acid (usually hydrochloric acid or sulfuric acid) as a catalyst, which may optionally contain salts.
  • the textile is impregnated with this strongly acidic liquor, which may contain up to 150 g / l and more of crosslinker, and dried to a residual moisture of 10 to 12 wt .-%. It is then allowed to linger for 20 to 24 hours at 30 to 35 ° C, the acid is neutralized and washed. After drying, usually the usual tools in the equipment for handle design are applied.
  • the object of the present invention was to provide a finishing process for cellulosic textile materials which, like the wet crosslinking process, provides the highest level of finishing but avoids its disadvantages.
  • drying (b) and condensation (c) steps may be separate or shared, i. in a reactor by heating and simultaneously removing the water vapor.
  • the principle of the method according to the invention can be applied both to fabric and to knitwear, with the amounts of crosslinker and crosslinking catalyst to be reduced in the latter case.
  • the process according to the invention can be transferred not only to pure cotton but also to other cellulose-containing materials. In blends with synthetic fibers such as polyester, it is due to the fiber protection and energy conservation of interest. Again, because of the lower proportion of cellulosic fibers, the amount of crosslinker and catalyst can be reduced.
  • Preferred amounts of crosslinker are in the case of fabric of 100% cellulosic material 90 to 175 g / l, in particular 110 to 160 g / l, in the case of knitwear of 100% cellulosic material 40 to 70 g / l, in particular 45 to 60 g / l, and in the case of mixtures of 30 to less than 100 wt .-% cellulosic fibers and greater than 0 to 70 wt .-% of synthetic fibers 45 to 120 g / l, in particular 55 to 100 g / l.
  • the last-indicated crosslinker amounts are particularly suitable for polyester-cotton blends in the weight% of about 50:50.
  • crosslinker For all above and below information, the amounts of crosslinker always refer to the corresponding solids content in g per liter of equipment fleet.
  • the crosslinkers are usually used as aqueous solutions having a solids content of 30 to 80 wt .-%, in particular 50 to 75 wt .-%.
  • N-methylol ethers I to be used as crosslinkers are obtained by customary reaction, usually in aqueous solution, of the corresponding N-methylol compounds of the general formula II with alcohols of the general formula III R 1 -OH (III) easily available.
  • the radical R 1 is an optionally interrupted by non-adjacent oxygen atoms C 1 -C 10 alkyl group such as -CH 2 CH 2 OCH 3 , -CH 2 CH 2 OCH 2 CH 3 or -CH 2 CH 2 OCH 2 CH 2 OCH. 3 , Further examples of R 1 are: n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl and 2-methoxyethyl; Of particular interest are the C 1 -C 3 alkyl groups ethyl, n-propyl, iso-propyl and especially methyl. Also of interest are those alkyl groups and alkyl groups interrupted by oxygen atoms which carry one, two, three or even more hydroxyl groups.
  • the radical R 2 denotes hydrogen, the group CH 2 OR 1 and in particular a C 1 -C 8 -alkyl radical which carry additional hydroxyl groups and / or C 1 -C 4 -alkoxy groups as substituents and by non-adjacent oxygen atoms and / or by C 1 -C 4 -alkyl groups bearing nitrogen atoms may be interrupted.
  • the radical R 3 is hydrogen, a C 1 -C 10 -alkyl radical, a C 1 -C 10 -alkoxy radical which may be interrupted by nonadjacent oxygen atoms, and in particular the group (-NR 2 -CH 2 OR 1 ).
  • N-methylol ethers I in which the radicals R 2 and R 3 are bonded to form a five- or six-membered ring.
  • R 3 (-NR 2 -CH 2 OR 1) can also two such rings may be condensed on to the amide nitrogens ⁇ -position carbon atoms of the radicals R 2 to form a bicyclic system.
  • DMDHEU 1,3-dimethylol-4,5-dihydroxyethyleneurea
  • one of the two methylol groups of the DMDHEU is etherified with a methyl radical, while the other methylol group is converted by reaction with a polyol selected from the group comprising ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3- and 1,4-butylene glycol, glycerol and polyethylene glycols of the formula HO (CH 2 CH 2 O) n H with 3 ⁇ n ⁇ 20, preferably diethylene glycol, is derivatized.
  • a polyol selected from the group comprising ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3- and 1,4-butylene glycol, glycerol and polyethylene glycols of the formula HO (CH 2 CH 2 O) n H with 3 ⁇ n ⁇ 20, preferably diethylene glycol, is derivatized.
  • a polyol selected from the group comprising ethylene glycol, di
  • the crosslinking catalyst is based on magnesium chloride as a sole component or as a main component.
  • a finishing liquor is used which contains 10 to 40 g / l, in particular 20 to 30 g / l of the crosslinking catalyst in the case of fabric of 100% cellulosic material, 5 to 15 g / l, in particular 8 to 13 g / l, of the crosslinking catalyst in the case of knit fabric of 100% cellulosic material or 5 to 30 g, in particular 8 to 25 g / l, of the crosslinking catalyst in the case of mixtures of 30 to less than 100 wt .-% cellulosic fibers and greater than 0 to 70 wt .-% contains synthetic fibers.
  • the above quantities in g are based on the proportions of magnesium chloride to magnesium chloride hexahydrate, in other catalyst components on the solids content of commercially available form.
  • the crosslinking catalyst used is preferably virtually pure magnesium chloride or mixtures of magnesium chloride and organic and / or inorganic acids such as citric acid, glycolic acid or acidic inorganic salts, e.g. Sodium tetrafluoroborate, a.
  • acidic e.g. Sodium tetrafluoroborate
  • finishing liquor containing the crosslinker and the crosslinking catalyst at (a) has a pH of from 3 to 6.5, in particular from 4 to 5.5.
  • auxiliaries can, if appropriate, significantly increase the quality of the finish again.
  • the inventive method allows at relatively low and thus gentle temperatures a rapid and complete condensation of the crosslinker on the textile. Normally, significantly longer condensation times are expected at the temperatures of step (c) of the process according to the invention.
  • the condensation according to step (c) is - depending on the respectively set temperature - usually after 15 seconds to 4 minutes, especially after 30 seconds to 3 minutes, completed.
  • the highly refined cellulosic textile material according to the invention has very high levels of smoothing and a very good crease recovery with unexpectedly low loss of tensile strength and low formaldehyde values.
  • Such results have hitherto been obtained only with the wet crosslinking process, although there the formaldehyde values are very high despite rewashing.
  • such a high amount of crosslinker as is used in the process according to the invention and in the wet crosslinking process normally leads to the destruction of the product because of the enormous loss of tear strength occurring.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (5)

  1. Procédé pour la fabrication de matériaux textiles contenant de la cellulose par apprêtage avec un agent de réticulation à base d'éthers de N-méthylol de formule générale I :
    Figure imgb0013
    dans laquelle :
    R1 représente un groupement alkyle en C1 à C10, qui est éventuellement interrompu par des atomes d'oxygène non adjacents et peut porter encore un ou plusieurs groupements hydroxyle,
    R2 désigne l'hydrogène, le groupement CH2OR1 ou un radical alkyle en C1 à C8, qui peut encore porter d'autres groupements hydroxyle et/ou des groupements alcoxy en C1 à C4 comme substituants et peut être interrompu par des atomes d'oxygène non adjacents et/ou des atomes d'azote non adjacents portant des groupements alkyle en C1 à C4, et
    R3 désigne l'hydrogène, un radical alkyle en C1 à C10, un radical alcoxy en C1 à C10, qui peut être interrompu par des atomes d'oxygène non adjacents, ou le groupement (-NR2-CH2OR1),

    où les radicaux R2 et R3 peuvent être liés à un cycle à cinq ou six éléments et, dans le cas où R3 = (-NR2-CH2OR1), en plus, deux de ces cycles peuvent être condensés en un système bicyclique via les atomes de carbone des radicaux R2, qui sont situés en position α par rapport aux atomes d'azote de l'amide, en présence d'un catalyseur de réticulation à base de chlorure de magnésium, caractérisé en ce que
    (a) on imprègne les matériaux textiles à apprêter de 50 à 100% en poids, par rapport aux matériaux textiles secs, d'un bain d'apprêtage contenant 70 à 250 g/l de l'agent de réticulation dans le cas de tissus constitués de 100% de matériau cellulosique, de 35 à 100 g/l de l'agent de réticulation dans le cas de tissus maillés constitués de 100% de matériau cellulosique ou de 35 à 150 g/l de l'agent de réticulation dans le cas de mélanges constitués de 30 à moins de 100% en poids de fibres cellulosiques et de plus de 0 à 70% en poids de fibres synthétiques,
    (b) on les sèche jusqu'à une humidité résiduelle de 3 à 10% en poids et
    (c) on effectue, à une température de 100 à 145°C, en présence du catalyseur de réticulation, la réticulation des matériaux textiles contenant de la cellulose en l'espace de 15 secondes à 4 minutes.
  2. Procédé de fabrication de matériaux textiles contenant de la cellulose selon la revendication 1, caractérisé en ce que l'on utilise en (a) un bain d'apprêtage, qui contient 10 à 40 g/l du catalyseur de réticulation dans le cas de tissus constitués de 100% de matériau cellulosique, 5 à 15 g/l du catalyseur de réticulation dans le cas de tissus maillés constitués de 100% de matériau cellulosique ou 5 à 30 g/l du catalyseur de réticulation dans le cas de mélanges composés de 30 à moins de 100% en poids de fibres cellulosiques et de plus de 0 jusqu'à 70% en poids de fibres synthétiques.
  3. Procédé de fabrication de matériaux textiles contenant de la cellulose selon la revendication 1 ou 2, caractérisé en ce que l'on utilise, comme catalyseur de réticulation, du chlorure de magnésium pratiquement pur ou des mélanges de chlorure de magnésium et d'acides organiques et/ou inorganiques.
  4. Procédé de fabrication de matériaux textiles contenant de la cellulose selon les revendications 1 à 3, caractérisé en ce que le bain d'apprêtage contenant l'agent de réticulation et le catalyseur de réticulation en (a) présente une valeur de pH de 3 à 6, 5.
  5. Procédé de fabrication de matériaux textiles contenant de la cellulose selon les revendications 1 à 4, caractérisé en ce que l'on utilise un agent de réticulation à base de 1,3-diméthylol-4,5-dihydroxyéthylène-urée, qui est éthéré au niveau des deux groupements méthylol, de manière symétrique ou non symétrique.
EP99967949A 1998-12-24 1999-12-16 Procede pour produire des materiaux textiles contenant de la cellulose Expired - Lifetime EP1141471B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19860204 1998-12-24
DE19860204A DE19860204A1 (de) 1998-12-24 1998-12-24 Verfahren zur Herstellung von cellulosehaltigen textilen Materialien
PCT/EP1999/010004 WO2000039384A1 (fr) 1998-12-24 1999-12-16 Procede pour produire des materiaux textiles contenant de la cellulose

Publications (2)

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EP1141471A1 EP1141471A1 (fr) 2001-10-10
EP1141471B1 true EP1141471B1 (fr) 2006-02-15

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EP99967949A Expired - Lifetime EP1141471B1 (fr) 1998-12-24 1999-12-16 Procede pour produire des materiaux textiles contenant de la cellulose

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EP (1) EP1141471B1 (fr)
JP (1) JP2002533585A (fr)
KR (1) KR100598664B1 (fr)
CN (1) CN1177094C (fr)
AT (1) ATE317924T1 (fr)
BR (1) BR9916534A (fr)
DE (2) DE19860204A1 (fr)
WO (1) WO2000039384A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE15711192T1 (de) 2014-03-24 2017-06-29 Basf Se Formulierungen und verfahren zur textilveredelung
KR101629252B1 (ko) * 2014-09-30 2016-06-10 (주)약진통상 염색방법

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1469273A1 (de) * 1965-09-25 1968-12-12 Basf Ag Verfahren zum Veredeln von Textilien
GB1243462A (en) * 1969-01-14 1971-08-18 Cotton Silk And Manmade Fibres Curing cross-linking agents on textiles
CH577584B5 (fr) * 1971-08-04 1976-07-15 Ciba Geigy Ag
US4396391B2 (en) * 1982-06-30 1993-03-16 Treating cellulose textile fabrics with dimenthylol dihydroyethyleneuree-polyol
US5160503A (en) * 1989-11-13 1992-11-03 West Point Pepperell Water-soluble blends of active methylene compounds and polyhydric alcohols as formaldehyde scavengers
DE19654739A1 (de) * 1996-12-30 1998-07-02 Basf Ag Gemischt-alkylierte bzw. -hydroxyalkoxyalkylierte methylolierte 4,5-Dihydroxy-imidazolidin-2-one

Also Published As

Publication number Publication date
DE59913133D1 (de) 2006-04-20
KR100598664B1 (ko) 2006-07-13
BR9916534A (pt) 2001-09-25
CN1331767A (zh) 2002-01-16
KR20010099872A (ko) 2001-11-09
CN1177094C (zh) 2004-11-24
JP2002533585A (ja) 2002-10-08
EP1141471A1 (fr) 2001-10-10
DE19860204A1 (de) 2000-06-29
WO2000039384A1 (fr) 2000-07-06
ATE317924T1 (de) 2006-03-15

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