EP2160489B1 - Procédé d'inhibition du jaunissement - Google Patents

Procédé d'inhibition du jaunissement Download PDF

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Publication number
EP2160489B1
EP2160489B1 EP08760908.7A EP08760908A EP2160489B1 EP 2160489 B1 EP2160489 B1 EP 2160489B1 EP 08760908 A EP08760908 A EP 08760908A EP 2160489 B1 EP2160489 B1 EP 2160489B1
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EP
European Patent Office
Prior art keywords
polyamide
carbodihydrazide
process according
employed
containing material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP08760908.7A
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German (de)
English (en)
Other versions
EP2160489A2 (fr
Inventor
Herbert Bachus
Christian Dörfler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CHT Germany GmbH
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CHT R Beitlich GmbH
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Publication of EP2160489A2 publication Critical patent/EP2160489A2/fr
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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
    • D06M13/422—Hydrazides
    • 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
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • 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
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • 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
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments

Definitions

  • the invention relates to highly yellowing-resistant polyamide-containing materials having surface finish containing carbodihydrazide, a method of finishing, and the use of appropriately prepared polyamide-containing materials.
  • Polyamides have a sufficiently high weathering and age resistance for a variety of applications. If desired, in outdoor applications by a special coloring such as carbon black, the durability can be further increased.
  • Dyeing with soot easily avoids the problem of yellowing, which frequently occurs in plastics - but does not eliminate it. This becomes particularly important if one is not interested in a very dark color of the finished plastic part. In such cases, a yellowing, caused either by oxidative aging processes or even by the thermal treatment during the manufacturing process is negatively noticeable.
  • thermosetting in which the product in question is subjected to a heat treatment with hot water, steam or dry heat and thus shrinks, whereby a subsequent undesirable dimensional change is prevented. Temperatures of 200 ° C and above are quite common here.
  • Another method is the molding in which the materials used are brought into a corresponding shape by the action of heat by a (press) tool (that is, by contact heat). This method is used, for example, in the production of brassieres.
  • the yellowing does not arise here only with untreated or optically brightened polyamide-containing material, which is usually yellow-white or milk-white depending on the type.
  • DE 19 631 381 A1 discloses cellulosic textile materials provided with an aqueous solution containing carba hydrazide.
  • Carbohydrazide is used as a discoloration inhibitor.
  • EP 0 436 470 B1 describes in this connection a photochemical stabilization of dyed polyamide fiber materials by the use of various complexes of bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic carbonyl compounds with copper as the central metal.
  • the use of the toxic heavy metal copper makes corresponding textile auxiliaries not only environmentally friendly but also health-friendly aspects of concern.
  • JP 60-81370 describes a process for treating textile products of polyamide fibers or polyamide fiber blends which have been dyed with acidic or metal-containing dyes.
  • the thus dyed textile products are treated with an antioxidant from the group of carbazides or hydrazines, in particular 1,6-hexamethylene bis (N, N-dimethylsemicarbazide) and adipic dihydrazide [ADH].
  • WO 2006/045721 A1 describes predominantly dicarboxylic acid bis-hydrazides, and of these in particular ADH, for improving the aging stability of undyed, optically brightened or natural or synthetic polyamide fiber materials dyed with reactive or disperse dyes, with the exception of metal complex dyes.
  • a disadvantage of the last two methods is in particular the fact that for a sufficient yellowing inhibition a relative large amount of textile adjuvant must be used. From the relatively low water solubility of the excipient, there is a further limitation.
  • the object of the present invention was therefore to provide a more effective antioxidant for yellowing inhibition. Furthermore, the antioxidant of the invention should have much lower environmental and / or harmful properties. Of course, both factors are mutually dependent, because an increased effectiveness implies the use of a lower amount of the antioxidant, which generally results in a significantly lower environmental and / or health burden.
  • the object underlying the invention is solved by a polyamide-containing material having a surface finish containing carbodihydrazide [CDH].
  • surface finishing means a refining of the material in question, in which case the CDH, in contrast to a surface coating, may also be on the inner surface of the material (caused, for example, by diffusion of the CDH under the equipment conditions).
  • the polyamide-containing material need not necessarily be an untreated or undyed material. It is also quite possible that it is an optically brightened material or colored with reactive, acid, disperse or metal complex dyes.
  • Preferred optical brighteners include the following compounds: stilbene-based compounds, especially alkylation products of 4,4'-diaminostilbene-2,2'-disulfonic acid; Compounds in which two heteroaromatic radicals are linked to one another via an ethylene bridge; Coumarin derivatives, in particular having an amino group or an N-heterocycle instead of the amino group; 1,3-diphenyl-2-pyrazolines; Naphthalimides, especially N-methyl-4-methoxynaphthalimide; Compounds containing a fused aromatic and a heteroaromatic, in particular 2,4-dimethoxy-6- (1'-pyrenyl) -1,3,5-triazine.
  • Preferred dyes are common dyes for polyamides, especially acid and metal complex dyes.
  • the polyamide-containing material may contain not only natural polyamides, in particular wool and / or silk, but also synthetic polyamides.
  • Examples of synthetic polyamides according to the present invention are: polyamide [PA] 4, PA 5, PA 6, PA 11, PA 12, PA 6.6, PA 6.10, PA 6.12, PACM 12, polyaramids such as Nomex and Kevlar, copolyamides such as PA 66/6 and PA 11/12 and block copolymers of polyamides and other polymers, in particular polyethers.
  • polystyrene resin in addition to polyamides, other polymers, in particular polyesters, polysaccharides, in particular cotton and / or viscose, polyurethanes and / or polyolefins, and also auxiliaries and / or effect substances customary for polymers, such as, for example, antistats, colorants, flame retardants, fillers Nucleating agents, pigments, reinforcing fibers and / or plasticizers possible.
  • other polymers in particular polyesters, polysaccharides, in particular cotton and / or viscose, polyurethanes and / or polyolefins, and also auxiliaries and / or effect substances customary for polymers, such as, for example, antistats, colorants, flame retardants, fillers Nucleating agents, pigments, reinforcing fibers and / or plasticizers possible.
  • the polyamide-containing material according to the invention can be present in the form of fibers, nonwovens, mesh, woven or knitwear and, as such, can also be further processed into secondary products.
  • the object underlying the invention is achieved by a process for finishing surfaces of polyamide-containing material, which comprises contacting the carbodihydrazide dissolved or dispersed in a liquid with the surface and subsequently removing the liquid ,
  • the carbodihydrazide solution or dispersion can be brought into contact with the surface by the exhaustion or, in particular, by padding process (also known as padding).
  • the padding process offers in comparison to the exhaust especially under Environmental aspects have great advantages, since it usually requires less solvent. In addition, it also ensures a more homogeneous application.
  • the carbodihydrazide can be applied in the process according to the invention before staining or optical brightening. However, it is preferred if this application step is followed by a possible lightening and / or coloring, since only then is the antioxidant used optimally utilized.
  • a solvent or dispersant for the carbodihydrazide is used in the process according to the invention advantageously water.
  • water have high solubility for CDH and the other common additives contained in the liquor, it also has the advantage of high environmental compatibility.
  • the amount of CDH in the liquor should be adjusted to a range of 0.1 g / L to 20 g / L, in particular from 0.5 to 10 g / L.
  • Lower concentrations have the disadvantage that the CDH-containing liquor would have to be applied several times to the polyamide-containing material in order to achieve the desired efficiency. Higher concentrations are not required for reasons of high efficacy.
  • the liquor used may contain other customary process or effect chemicals, in particular wetting agents, plasticizers, oleo and / or hydrophobizing additives or thickeners.
  • a heat-setting or molding step may be followed, in which the antioxidant action of the carbodihydrazide is utilized. It is possible that the fleet mainly removing solvents and / or dispersants in the course of these thermal processing steps to remove what is of course favored insofar as can be reduced in this way, the number of required process steps. However, the solvent and / or dispersant can also be removed beforehand in a separate step.
  • Another embodiment of the present invention is the use of a solution or dispersion containing a carbodihydrazide as a textile auxiliary.
  • CDH-treated textiles based on polyamide have a very high stability in the yellowing inhibition against thermal influences and / or oxidizing agents.
  • thermal influences are here in particular treatment method of polyamide-containing materials to understand, which are carried out at higher temperatures, such as thermosetting or Molden.
  • Oxidizing agents are to be understood as meaning in particular nitrogen oxides, ozone or chlorine-containing oxidizing agents.
  • Polyamide 6.6 knit fabric was lightened at a liquor ratio of 1:10 with 1.0% Tuboblanc® MA.
  • the pH was adjusted to 4 with acetic acid, the treatment was carried out at 95 ° C and 30 minutes. Thereafter, rinsed hot and cold and dried at 120 ° C. Subsequently, the pad at 100% liquor pickup was treated with the stated amount of antioxidant, the pH was adjusted to 5 with acetic acid. It was dried again at 120 ° C. After thermofixing, basic white [GW] and fluorescence [F] are assessed.
  • Polyamide 6.6 knitwear was dyed at a liquor ratio of 1:10 with acid dyes.
  • 2 g / L Sarabid EP and 0.5 g / L Meropan EF were initially added after 10 min 0.02% of a Bezanyl ® -Säurefarbstoffes, after a further 10 min at 2 ° C / min to 98 ° C heated , Treated at this temperature for 30 minutes, then cooled to 60 ° C. at 2 ° C./min and rinsed.
  • ADH and CDH worked very efficiently compared to the samples without antioxidant, 1 g / L ADH improved the result, good results were obtained only with 2 g / L ADH or CDH according to the invention already at 0.5 to 0.75 g / L , 1 g / L CDH worked best.
  • the treatment was carried out analogously to Example 3, but instead of Moldens at 200 ° C and 210 ° C in each case 30 or 60 s heat-set.
  • the treatment was carried out analogously to Example 4, but first the antioxidant was applied, then heat-set and dyed at the end.
  • Example 7 Storage stability and efficacy of aqueous CDH
  • Example 1 The 10-fold amount of a 10% solution, which was previously stored for 2 months at room temperature, was used analogously to Example 1 instead of pure CDH. All results are in the range of Example 1, ie a 10% solution of CDH was sufficiently storage stable to settlements and scored at the appropriate use concentration in the textile application, the same effect.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Claims (20)

  1. Matériau contenant du polyamide et portant une finition de surface contenant du carbodihydrazide.
  2. Matériau selon la revendication 1, caractérisé en ce que ledit matériau contenant du polyamide est teint, non teint ou azuré optiquement.
  3. Matériau selon l'une des revendications 1 ou 2, caractérisé en ce que ledit matériau contenant du polyamide contient des polyamides naturels, notamment de la laine et/ou de la soie.
  4. Matériau selon l'une des revendications 1 ou 2, caractérisé en ce que ledit matériau contenant du polyamide contient des polyamides synthétiques.
  5. Matériau selon l'une quelconque des revendications 1 à 4, caractérisé en ce que ledit matériau contenant du polyamide contient d'autres polymères, notamment des polyesters, des polysaccharides, des polyuréthanes et/ou des polyoléfines.
  6. Matériau selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il se présente sous la forme de fibres, de tissus non tissés, de tissus de mailles, de tissus ou de tricots.
  7. Procédé pour la finition de surfaces de matériaux contenant du polyamide, caractérisé en ce que l'on met le carbodihydrazide dissout ou dispersé dans un liquide en contact avec ladite surface, suivi de l'enlèvement du liquide.
  8. Procédé selon la revendication 7, caractérisé en ce que la solution ou dispersion de carbodihydrazide est appliquée à la surface par le procédé d'épuisement ou, notamment, par des procédés de foulardage.
  9. Procédé selon l'une des revendications 7 ou 8, caractérisé en ce que ledit carbodihydrazide est appliquée avant ou après, notamment après, la teinture et/ou l'azurage optique.
  10. Procédé selon l'une quelconque des revendications 7 à 9, caractérisé en ce qu'un matériau contenant du polyamide qui contient des polyamides naturels, notamment de la laine et/ou de la soie, est utilisé.
  11. Procédé selon l'une quelconque des revendications 7 à 9, caractérisé en ce qu'un matériau contenant du polyamide qui contient des polyamides synthétiques est utilisé.
  12. Procédé selon l'une quelconque des revendications 7 à 11, caractérisé en ce qu'un matériau contenant du polyamide qui contient d'autres polymères, notamment des polyesters, des polysaccharides, des polyuréthanes et/ou des polyoléfines, est utilisé.
  13. Procédé selon l'une quelconque des revendications 7 à 12, caractérisé en ce que des fibres, des tissus non tissés, des tissus de mailles, des tissus ou des tricots sont utilisés en tant que matériau contenant du polyamide.
  14. Procédé selon l'une quelconque des revendications 7 à 13, caractérisé en ce que de l'eau est utilisée comme solvant ou dispersant pour le carbodihydrazide.
  15. Procédé selon l'une quelconque des revendications 7 à 14, caractérisé en ce qu'un bain contenant une quantité de 0,1 g/l à 20 g/l, notamment de 0,5 à 10 g/l, de carbodihydrazide est utilisé.
  16. Procédé selon l'une quelconque des revendications 7 à 15, caractérisé en ce qu'un bain contenant des produits chimiques de traitement ou d'effet habituels, notamment des agents mouillants, des plastifiants, des additifs oléophobants et/ou hydrophobants ou des agents épaississants, est utilisé.
  17. Procédé selon l'une quelconque des revendications 7 à 16, caractérisé en ce que le textile est thermofixé ou préformé après le traitement au carbodihydrazide.
  18. Utilisation de carbodihydrazide ou d'une solution ou dispersion qui le contient comme agent auxiliaire textile pour la finition de surfaces de matériaux contenant du polyamide.
  19. Utilisation selon la revendication 18 pour la stabilisation de textiles contre les influences thermiques et/ou les oxydants.
  20. Utilisation selon la revendication 19 pour la stabilisation de textiles contre les oxydes d'azote, l'ozone ou les oxydants contenant du chlore.
EP08760908.7A 2007-06-23 2008-06-12 Procédé d'inhibition du jaunissement Active EP2160489B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007028997A DE102007028997A1 (de) 2007-06-23 2007-06-23 Verfahren zur Vergilbungsinhibierung
PCT/EP2008/057364 WO2009000660A2 (fr) 2007-06-23 2008-06-12 Procédé d'inhibition du jaunissement

Publications (2)

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EP2160489A2 EP2160489A2 (fr) 2010-03-10
EP2160489B1 true EP2160489B1 (fr) 2016-05-25

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EP08760908.7A Active EP2160489B1 (fr) 2007-06-23 2008-06-12 Procédé d'inhibition du jaunissement

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EP (1) EP2160489B1 (fr)
DE (1) DE102007028997A1 (fr)
WO (1) WO2009000660A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105133313B (zh) * 2015-10-15 2017-09-19 东华大学 一种用于尼龙的抗黄变剂
CN114481624B (zh) * 2022-02-08 2024-05-03 东莞市中纺化工有限公司 一种抗黄变添加剂及其制备方法与应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6081370A (ja) 1983-10-07 1985-05-09 日華化学株式会社 繊維製品の処理方法
US5069681A (en) 1990-01-03 1991-12-03 Ciba-Geigy Corporation Process for the photochemical stabilization of dyed polyamide fibres with foamed aqueous composition of copper organic complexes
US5294735A (en) * 1991-03-04 1994-03-15 Ciba-Geigy Corporation Semicarbazides and the use thereof for stabilizing polyamide fibre materials and the dyeings produced thereon
AT402518B (de) * 1995-08-03 1997-06-25 Chemie Linz Gmbh Mit guanidin- oder ethylendiaminsalz flammgehemmte zellulose-materialien, enthaltend einen verfärbungsinhibitor
US20090158531A1 (en) 2004-10-28 2009-06-25 Edvard Ham Method of improving thermal stability

Also Published As

Publication number Publication date
DE102007028997A1 (de) 2008-12-24
WO2009000660A2 (fr) 2008-12-31
WO2009000660A3 (fr) 2009-07-30
EP2160489A2 (fr) 2010-03-10

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