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WO1996011224A1 - Utilisation de dispersions aqueuses de polyamides dispersibles dans l'eau servant d'apprets - Google Patents

Utilisation de dispersions aqueuses de polyamides dispersibles dans l'eau servant d'apprets Download PDF

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Publication number
WO1996011224A1
WO1996011224A1 PCT/EP1995/003810 EP9503810W WO9611224A1 WO 1996011224 A1 WO1996011224 A1 WO 1996011224A1 EP 9503810 W EP9503810 W EP 9503810W WO 9611224 A1 WO9611224 A1 WO 9611224A1
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WO
WIPO (PCT)
Prior art keywords
mol
acid
water
atoms
polyamides
Prior art date
Application number
PCT/EP1995/003810
Other languages
German (de)
English (en)
Inventor
Herbert Fisch
Norbert Sendhoff
Jörg Breitenbach
Heinz Leitner
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1996011224A1 publication Critical patent/WO1996011224A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides

Definitions

  • the invention relates to the use of aqueous dispersions of water-dispersible polyamides as sizing agents for warp yarns.
  • Textile yarns which consist of a large number of individual threads and which are used as warp yarns in the weaving process are usually treated with a sizing agent which connects the individual threads of the yarns to one another and thereby strengthens and strengthens the warp yarns, so that they withstand the strong mechanical stresses Withstand the weaving process better than non-sized yarns.
  • EP-A-0 332 980 discloses polyester dispersions which, by condensing aromatic dicarboxylic acids with at least one diol to form prepolymers with an acid number of 2 to 8, react the prepolymers with, for example, tricarboxylic acids to form a polyester an acid number of 40 to 60 and dispersing the polyester in water with the formation of aqueous dispersions can be used in the form of ammonium salts as sizing agents for sizing filament warp threads.
  • the sulfonate group-carrying polyamides are easily dispersible in water. They are suitable, for example, for the production of aqueous dispersions which contain 1 to 70% by weight of such a polyamide in dispersed form.
  • the dispersions are used, for example, as film formers in hair fixatives.
  • the object of the present invention is to provide sizing agents which give films with good mechanical properties and good heat resistance.
  • the sizing agent should be easy to wash out of the warp yarns after the weaving process.
  • the object is achieved according to the invention by using aqueous dispersions of water-dispersible polyamides which are obtainable by condensation of
  • monoaminocarboxylic acids having 2 to 12 carbon atoms or their lactams are used as compounds of group (a).
  • Individual examples of such compounds are ⁇ -aminoundecanoic acid, ⁇ -caprolactam, capoyl lactam, laurolactam and enantlactam.
  • the lactams mentioned can also be used in the form of the monoaminocarboxylic acids.
  • the use of ⁇ -caprolactam is particularly preferred.
  • the mixtures which are subjected to the condensation contain, for example, 30 to 94.8, preferably 52 to 85 and in particular 60 to 80 mol% of a compound of component (a) or mixtures of 2 or more compounds (a).
  • diamines are used in the condensation which contain 2 to 18 carbon atoms.
  • the diamines can differ from aliphatic, cycloaliphatic or aromatic compounds. conduct. Examples of suitable diamines are the following compounds: ethylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, piperazine, 4,4'-diaminodicyclohexylmethane, 2,2- (4,4'- Diaminodicyclohexylpropane, 3, 3 '-dimethyl-4, 4'-diaminodicyclohexylmethane, 2, 2, 4-trimethyl-hexamethylenediamine, 2-butyl-2-ethyl-l, 5-pentanediamine and 4, 7-dioxadecane-l, 10-
  • the diamines can be used individually or as a mixture with one another in the preparation of the water-dispersible polyamides. Hexamethylenediamine from group (b
  • Suitable compounds of component (c) are those dicarboxylic acids which carry a sulfonate group as substituents.
  • the sulfonate group is preferably in the form of the sodium, potassium, lithium or ammonium salts.
  • Suitable dicarboxylic acids carrying sulfonate groups are, for example, the alkali or ammonium salts of aliphatic or aromatic dicarboxylic acids such as sulfosuccinic acid or 5-sulfoisophthalic acid.
  • the sodium salt of 5-sulfoisophthalic acid is particularly preferably used as component (c).
  • the compounds of component (c) are used in the condensation in amounts of 2.6 to 7, preferably 2.9 to 6.5 mol%.
  • Component (d) may be other dicarboxylic acids that are different from compounds ((c).
  • Compounds (d) are therefore free from sulfonate groups.
  • These compounds are aliphatic or aromatic dicarboxylic acids, eg oxalic acid, malonic acid, Adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid or suberic acid
  • Suitable aromatic dicarboxylic acids have, for example, 8 to 16 carbon atoms, for example terephthalic acid, isophthalic acid or substituted aromatic carboxylic acids such as 3-tert-butyl-isophthalic acid, 3,3'- or 4, 4'-diphenyldicarboxylic acid, 3,3'- or 4,4'-diphenylmethane dicarboxylic acid, 3,3'- or 4,4'-diphenylsulfone dicarboxylic acid, 1,4- or 2,6-naphthalenedicarboxylic acid or
  • (d) contain 3 to 25 mol% of terephthalic acid or isophthalic acid.
  • the water-dispersible polyamides to be used according to the invention are prepared by condensation of the compounds (a), (b), (c) and (d) by known methods.
  • the condensation can either be carried out batchwise in a batch process or else continuously.
  • an aqueous solution of the monomers is placed in an autoclave and, after the autoclave has been closed, it is heated to temperatures in the range from, for example, 240 to 300 ° C.
  • a pressure of 10 to 50, mostly 15 to 30 bar is reached, which can be kept constant for up to 4 hours by releasing excess water vapor.
  • the heating of the aqueous monomer solution to the reaction temperature takes, for example, 0.5 to 3 hours.
  • the autoclave After the condensation has ended, which takes, for example, 1 to 5 hours in the temperature range from 240 to 300 ° C., the autoclave is depressurized at constant temperature within a period of 0.5 to 3 hours to normal pressure. The polymer melt is then discharged from the autoclave, cooled by air or nitrogen cooling and granulated.
  • the polyamides obtainable in this way have, for example, a viscosity number of 25 to 110, preferably 30 to 80 ml / g, measured on a 0.5% strength by weight solution in 96% strength sulfuric acid.
  • the polyamides to be used according to the invention as sizing agents are easily dispersible in water.
  • a polyamide granulate is introduced into water and the mixture is stirred.
  • the polyamides are completely dispersed in the aqueous medium within a period of, for example, 0.5 to 3 hours. Dispersions are usually produced, the solids contents from 1 to 70, preferably have from 10 to 40% by weight.
  • the polyamides are preferably dispersed in water, but mixtures of water and a water-miscible solvent can also be used, for example alcohols such as ethanol, isopropanol, n-propanol, n-butanol and isobutanol or acetone are suitable as water-miscible solvents.
  • the amount of water-miscible solvent used, if any, is 2 to 50% by weight, based on water.
  • the polyamides dispersed in such water / organic solvent mixtures can also be used according to the invention as sizing agents.
  • the concentration of the aqueous dispersion of water-dispersible polyamides is preferably 10 to 40% by weight.
  • the translucency of the dispersions of water-dispersible polyamides to be used according to the invention is, for example, 50 to 99% and is usually above 60%.
  • the diameter of the dispersed particles is, for example, 30 to 200, preferably 30 to 140 nm.
  • the polyamide dispersions can of course also be produced in other mixing units in which the constituents to be mixed are subjected to greater shear.
  • the pH of the aqueous dispersions to be used according to the invention is, for example, 5 to 12.
  • the dispersions of water-dispersible polyamides described above are used according to the invention as sizing agents for warp yarns.
  • the size coating on the yarn is, for example, 0.5 to 10, preferably 1 to 5% by weight.
  • the aqueous dispersions of water-dispersible polyamides to be used according to the invention are suitable, for example, for sizing smooth and textured polyester yarns and polyamide yarns, preferably for polyamide yarns PA6 and PA6.6 of all finenesses.
  • the sizes to be used according to the invention have good adhesive strength and are easy to wash out. They can also be used to size yarns that are woven on water jet looms.
  • the weaving of the threads sized with the sizes according to the invention is also possible on all other weaving machines, for example air nozzles, grippers, projectile and shuttle weaving machines. Unless otherwise stated, the percentages in the examples are percentages by weight.
  • the K values of polymers were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932).
  • a 5 liter laboratory autoclave is charged with 2 kg of the components (a) to (d) given in Table 1 in the amounts also given there in 1500 ml of water.
  • the autoclave is closed and heated to a temperature of 280 ° C. within 1 hour, the resulting pressure of approx. 20 bar being kept constant by releasing excess water vapor. Pressure and temperature are kept unchanged for another hour.
  • the autoclave is then decompressed to normal pressure within 1 hour while maintaining the temperature of the reaction product at 280 ° C.
  • the reaction mixture is then post-condensed in a stream of nitrogen for 2 hours.
  • the melt obtained is pressed through a nozzle, and the strand is cooled and granulated in an air bed. 400 g of the granules are dispersed in 600 g of water at room temperature with stirring. The following tests were carried out on the granules:
  • Viscosity number [ml / g] 71.5 79 87 112 63 85 - 72 ⁇ [mPas] 98 122 140 110 200 110> 1000
  • the layer means 7 and 8 produced for comparison are not suitable for practical use.
  • the sizing agent 7 with a content of 5-sulfoisophthalic acid sodium salt of 2 mol% can no longer be converted directly into a dispersion form, while the layering agent 8 with a content of 7.5 mol% of 5-sulfoisophthalic acid sodium salt due to the high viscosity, it can only be produced with solid concentrations significantly below 10% by weight.
  • aqueous polyacrylic acid with a pH of 1.5, a molar mass of approx. 250,000 and a viscosity of 1000 mPas (23 ° C, Brookfield viscometer) and a K value according to Fikentscher of 110 (1% in water at 25 ° C).
  • the thread closure, moisture sensitivity and washability were determined as the application properties of the copolymers to be used according to the invention.
  • the thread closure is a measure of the quality of a size in relation to the protection and stabilization of the thread.
  • the Shirley filament counter is used to determine the thread closure, in which the filament thread is cut before and after finishing and the number of free, unglued individual filaments is determined from the pulses counted during cutting.
  • the raw yarn has a manra value of 100, i.e. 100% of the individual filaments are unglued. The lower the manra value, the more individual filaments are glued to the interface and the better the thread closure and the thread adhesion and thus the achievable weaving effect.
  • test yarns made of polyamide 66dtex 78f 23Z20 with 2 and 4% sizing layers were used, which were measured both directly with the Shirley filament counter (Manra value MO in Table 2) and before the measurement on which Reutlingen weavers were exposed to 100 stress cycles (Manra value M 100 in Table 2).
  • the condensates according to the invention show good thread closure (Table 2) and good pendulum hardness values (Table 3).
  • the pen hardness values of the comparative examples are clearly below those of the polymers to be used according to the invention.
  • the K / S value indicates the size content relative to other samples.
  • a small K / S value corresponds to a low residual size content.
  • the K / S value was listed in Textile Practice International, July 1991, pages 644-646.
  • a size under laboratory conditions should be used in a neutral washing recipe (e.g. 80 ° C,
  • Wash liquor distilled water
  • AHIBA-Texomat a low washing mechanism
  • one alkaline washing recipe ie 80 ° C, 2 g / 1 soda, 1 g / 1 wetting agent
  • the condensates to be used according to the invention show poor washability in neutral wash liquor and good washability in alkaline wash liquor. In contrast to the commercially available polymers according to the comparative example, they are therefore suitable for water jet weaving machines.
  • Example cf. Sizing 10 min, 80 ° C, 10 min, 80 ° C

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyamides (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne l'utilisation, comme apprêts pour fils de chaîne, de dispersions aqueuses de polyamides dispersibles dans l'eau obtenues par condensation de (a) entre 30 et 94,8 % en moles d'un acide monoaminocarboxylique ayant entre 2 et 12 atomes de C ou son lactame, (b) entre 2,6 et 37 % en moles d'une diamine ayant entre 2 et 18 atomes de C, (c) entre 2,6 et 7 % en moles d'un acide dicarboxylique substitué avec des groupes sulfonate et (d) entre 0 et 30 % en moles d'un acide dicarboxylique différent de (c) ayant entre 2 et 16 atomes de C, et par dispersion des condensats dans un milieu aqueux.
PCT/EP1995/003810 1994-10-06 1995-09-26 Utilisation de dispersions aqueuses de polyamides dispersibles dans l'eau servant d'apprets WO1996011224A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4435687.0 1994-10-06
DE19944435687 DE4435687A1 (de) 1994-10-06 1994-10-06 Verwendung wäßriger Dispersionen von wasserdispergierbaren Polyamiden als Schlichtemittel

Publications (1)

Publication Number Publication Date
WO1996011224A1 true WO1996011224A1 (fr) 1996-04-18

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Application Number Title Priority Date Filing Date
PCT/EP1995/003810 WO1996011224A1 (fr) 1994-10-06 1995-09-26 Utilisation de dispersions aqueuses de polyamides dispersibles dans l'eau servant d'apprets

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DE (1) DE4435687A1 (fr)
WO (1) WO1996011224A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU68507A1 (fr) * 1972-09-28 1973-12-07
FR2256195A1 (fr) * 1973-12-26 1975-07-25 Asahi Chemical Ind
EP0394505A1 (fr) * 1985-03-15 1990-10-31 The Dow Chemical Company Polyamides et polyurées aromatiques sulfonés réticulables
WO1993019239A1 (fr) * 1992-03-17 1993-09-30 Monsanto Company Polyamides sulfones

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU68507A1 (fr) * 1972-09-28 1973-12-07
FR2256195A1 (fr) * 1973-12-26 1975-07-25 Asahi Chemical Ind
EP0394505A1 (fr) * 1985-03-15 1990-10-31 The Dow Chemical Company Polyamides et polyurées aromatiques sulfonés réticulables
WO1993019239A1 (fr) * 1992-03-17 1993-09-30 Monsanto Company Polyamides sulfones

Also Published As

Publication number Publication date
DE4435687A1 (de) 1996-04-11

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