EP0765414B1 - Thermally stable textile smoothing agents - Google Patents

Thermally stable textile smoothing agents Download PDF

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Publication number
EP0765414B1
EP0765414B1 EP95921839A EP95921839A EP0765414B1 EP 0765414 B1 EP0765414 B1 EP 0765414B1 EP 95921839 A EP95921839 A EP 95921839A EP 95921839 A EP95921839 A EP 95921839A EP 0765414 B1 EP0765414 B1 EP 0765414B1
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EP
European Patent Office
Prior art keywords
fatty acid
lubricants
polyol fatty
acid esters
esters
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.)
Expired - Lifetime
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EP95921839A
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German (de)
French (fr)
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EP0765414A1 (en
Inventor
Raymond Mathis
Norbert Bialas
F. Norman Tuller
Richard P. Crews
Elbert H. Mudge
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Cognis IP Management GmbH
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Henkel AG and Co KGaA
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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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
    • D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
    • 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
    • D06M13/10—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 oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • 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
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • 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
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the invention relates to thermostable textile smoothing agents based on Polyol fatty acid esters, with small amounts to increase the thermal stability on special esters of thiocarboxylic acids.
  • the present invention relates to spin finishes using this textile Contain smoothing agents as well as a method for producing the thermostable textile smoothing agent.
  • spin finishes are used used. These spin finishes all contain so-called textile smoothing agent to avoid friction between filaments or fibers and to minimize between filaments and governing bodies.
  • textile Smoothing agents are increasingly being used in polyol carboxylic acid esters.
  • thermal stability thermal stability
  • antioxidants such as butylated hydroxytoluene (BHT) to use because such connections are already in small up to medium quantities effectively improve the thermal stability.
  • BHT butylated hydroxytoluene
  • Unfortunately have BHT and related antioxidants at temperatures, that occur in the manufacture and processing of textile fibers, a relatively high volatility. This leads to this class of antioxidants quickly evaporates and therefore its purpose is an oxidative To prevent damage to the textile smoothing agent, only initially, however cannot meet for the whole process.
  • antioxidants e.g. B. the commercially known Irganox R 1010 known to those skilled in the art, the volatility of which is relatively low.
  • this procedure has the disadvantage that this group of antioxidants has only a limited solubility in the esters. It follows from this that the required concentration of dissolved antioxidant cannot be achieved to a sufficient extent.
  • WO-A-9113134 discloses a method for improving the solubility of antioxidants in smoothing agents, the antioxidant being incorporated into a carrier medium via covalent bonds.
  • the teaching of WO 91/13134 in its preferred embodiment relates to the fact that so-called "superstable lubricants" are obtained when the proportion of the covalently bound antioxidant in the carrier medium is in the range from greater than 0 to 30% by weight.
  • the proportion of the covalently bound antioxidant in the carrier medium is in each case 10 or 20% by weight.
  • An example of a particularly suitable product is a textile smoothing agent in which 10% by weight of Irganox R 1010 is covalently bonded to pentaerythritol pelargonate as the carrier. From an economic and ecological point of view, however, it is desirable to minimize the antioxidant content.
  • the object of the present invention was to provide thermostable textile smoothing agents To provide the disadvantages of the known prior art avoid technology.
  • the aim was to create thermostable textiles Developing smoothing agents that contain a minimal amount of antioxidants need.
  • the first object of the present invention are therefore thermostable textile smoothing agent, suitable for spin finishes, based on polyol fatty acid ester, characterized in that to increase the thermal stability in amounts of 0.05 to 8% by weight, based on polyol fatty acid esters
  • the polyols and the fatty acids of the polyol fatty acid esters can be saturated or olefinically unsaturated and straight-chain with respect to their carbon skeleton or be branched.
  • the radicals R 1 to R 4 can be saturated or olefinically unsaturated, straight-chain or branched, insofar as this is an alkyl, alkylene, cycloalkylene or cycloalkyl group or the alkyl part of an alkaryl group.
  • Polyols are polyvalent in the context of the present invention Alcohols understood with at least 2 OH groups.
  • the chemical constitution the polyols are not subject to any particular restrictions, i.e. they can be straight or branched.
  • the polyols selected from that of glycerol, trimethylolpropane, neopentyl glycol and pentaerythritol formed group.
  • the fatty acid residues of the polyol fatty acid esters are preferably derived from fatty acids with 8 to 18 carbon atoms, which are also preferably saturated.
  • the best effects are achieved in the context of the present invention if those with 8 to 10 carbon atoms are used as fatty acids.
  • the latter acids are known to those skilled in the art as caprylic acid, pelargonic acid and / or capric acid. These acids can be used either individually or in mixtures. Mixtures of C 8 and C 10 fatty acids are known as so-called pre-fatty acids.
  • esters of thiocarboxylic acids those are preferred in which the thiocarboxylic acids of the general formula (I) and / or (II) with monofunctional aliphatic alcohols with 1 to 22 carbon atoms, neopentyl glycol, Glycerin, trimethylolpropane or pentaerythritol are esterified.
  • neopentyl glycol, glycerin, trimethylol propane and pentaerythritol can be pure or mixed Trade esters.
  • “Pure” esters are understood to mean such esters, in which all hydroxyl groups of the polyfunctional alcohols with one or esterified several thiocarboxylic acids of the general formula (I) and / or (II) are.
  • “Mixed” esters are understood to mean those esters in which have at least one hydroxyl group with a thiocarboxylic acid of the general Formula (I) or (II) is esterified. The other hydroxyl groups are then related to fatty acids with 6 to 22 carbon atoms as they are are described with the polyol fatty acid esters. Particularly preferred are the esters of monofunctional aliphatic alcohols described type and the "pure" esters of pentaerythritol.
  • monofunctional aliphatic alcohols are particularly suitable for n- and i-butanol, 2-ethylhexanol, isotridecyl alcohol, lauryl alcohol, isostearyl alcohol and / or oleyl alcohol.
  • R 1 denotes an alkyl group with 6 to 18 C atoms
  • R 2 denotes an alkylene group with 1 or 2 C atoms.
  • Particularly suitable examples are ⁇ -laurylthiopropionic acid (C 12 H 25 SCH 2 CH 2 COOH) and ⁇ -octylthiopropionic acid (C 8 H 17 SCH 2 CH 2 COOH).
  • R 3 and R 4 are an alkylene group having 2 carbon atoms, ie thiodipropionic acid (HOOCCH 2 CH 2 SCH 2 CH 2 COOH).
  • esters of thiocarboxylic acid are commercially available compounds that but are also easily accessible by known esterification reactions.
  • the mixed esters can easily be obtained by transesterification of the pure thioates obtained with the fatty acids described.
  • the esters of thiocarboxylic acids in an amount of 0.05 to 8 % By weight - based on the polyol fatty acid esters. It is preferred, the esters of thiocarboxylic acids in an amount of 0.5 to 5 % By weight, in particular from 1.0 to 3.0% by weight, to be used.
  • This indication of Amounts used relate to the amounts defined above pure esters of thiocarboxylic acids. With mixed esters of thiocarboxylic acids are higher according to the content of thiocarboxylic acids in the ester Use quantities. The esters of thiocarboxylic acids are converted into the polyol fatty acid esters registered.
  • esters of thiocarboxylic acids in the polyol fatty acid esters stirred in at temperatures of 20 to 80 ° C.
  • Tin-based compounds such as are suitable as transesterification catalysts Tin octoate and sodium methylate.
  • the transesterification catalysts are in an amount of 0.01 to 2 wt.% - Based on the total amount of polyol fatty acid ester and esters of thiocarboxylic acids.
  • antioxidants are additionally added as an additive to the smoothing agents according to the invention. These antioxidants are added with or after the entry of the esters of thiocarboxylic acids, which is preferably carried out at temperatures from 90 to 170 ° C. in the presence of the transesterification catalysts.
  • Another object of the present invention is therefore a process for the preparation of thermostable textile smoothing agents based on polyol fatty acid esters, characterized in that the polyol fatty acid esters with 0.05 to 8 wt.% - Based on polyol fatty acid esters - on esters of thiocarboxylic acids of the general formula (I ) and / or (II) R 1 - S - R 2 - COOH HOOC - R 3 - S - R 4 - COOH wherein R 1 is a monovalent radical and R 2 , R 3 , R 4 are identical or different divalent radicals of alkanes, cycloalkanes, aromatics or alkyl aromatics having 1 to 22 carbon atoms. at temperatures of 90 to 170 ° C in the presence of a transesterification catalyst, optionally in the presence of additional antioxidants.
  • the additional antioxidants can be present in the process from the beginning or can be added during the process or can also be added subsequently.
  • Suitable antioxidants are butylated hydroxytoluene, dialkyl or Diaryl phosphonates, trialkyl or triaryl phosphites, ascorbic or citric acid and their derivatives and especially sterically hindered Phenols.
  • the sterically hindered are particularly preferred as additional additives Phenols of the structure (A-1 and / or A-6) used.
  • the additional additives ensure that the inherently good thermal stability of the textile smoothing agents according to the invention is further improved in a synergistic manner. This can be seen, inter alia, from the fact that much smaller amounts of the antioxidants have to be added than described, for example, in WO 91/13134 (10 to 20% by weight) in order to achieve comparable thermostabilities. For example, even amounts of 1.0% by weight of the sterically hindered Irganox R 1010 phenol - based on the total amount of polyol fatty acid ester and ester of thiocarboxylic acids - result in excellent thermostabilities.
  • the antioxidants in relation to the esters of thiocarboxylic acids in an amount of Add 1: 1 to 1: 4.
  • the sterically hindered phenols Particularly good results are obtained when the amount of additional antioxidants d) 10 to 50% by weight, based on the esters of thiocarboxylic acids , the range from 20 to 30% by weight being particularly preferred.
  • the textile smoothing agents according to the invention can because of their high thermal stability among other things can be used in spin finishes.
  • Another subject of the present Invention are therefore spin finishes for synthetic filaments, characterized in that they have the described thermostable contain textile smoothing agents.
  • the textile smoothing agent in turn which may contain additional antioxidants.
  • the spin finishes contain at least about 35% by weight of the textile smoothing agents.
  • Other components of the spin finishes can be emulsifiers, wetting agents and / or antistatic agents and the auxiliaries known from the prior art such as thread closing agents, pH regulators, bactericides and / or Be anti-corrosion agent.
  • Suitable emulsifiers, wetting agents and / or antistatic agents are anionic, cationic and / or nonionic surfactants, such as mono- and / or diglycerides, for example glycerol mono- and / or glycerol dioleate, alkoxylated, preferably ethoxylated and / or propoxylated fats or oils, fatty alcohols with 8 to 24 carbon atoms and / or C 8-18 alkylphenols, for example addition products of 25 mol ethylene oxide onto castor oil and / or addition products of 8 mol propylene oxide and 6 mol ethylene oxide onto C 16-18 fatty alcohols, if desired alkoxylated C 8- 24 fatty acid mono- and / or diethanolamides, for example - optionally ethoxylated - oleic acid mono- and / or diethanolamide, tallow fatty acid mono- and / or diethanolamide and / or coconut fatty acid mono- and / or
  • alkyl sulfosuccinates for example sodium dioctyl sulfosuccinate and / or amine oxides, for example dimethyldodecylamine oxide.
  • an antistatic can act as an emulsifier at about the same time.
  • Suitable thread closure agents are the polyacrylates, fatty acid sarcosides and / or copolymers with maleic anhydride known from the prior art.
  • Suitable pH regulators are C 1-4 carboxylic acids and / or C 1-4 hydroxycarboxylic acids, e.g. B. acetic acid and / or glycolic acid, alkali hydroxides such as potassium hydroxide and / or amines such as triethanolamide, the presence of bactericides and / or anti-corrosion agents is possible.
  • the spin finishes according to the invention can be mixed intensively the textile smoothing agent according to the invention, optionally with the emulsifiers, Wetting agents, antistatic agents and, if necessary, with the usual additives Produce approx. 18-25 ° C.
  • the spin finishes are applied in the form of their aqueous dispersions to the synthetic filament fibers immediately after exiting the spinneret.
  • the spin finishes which have a temperature between 18 and 60 ° C, are applied with the help of application rollers or dosing points using suitable applicators.
  • the spin finishes according to the invention contain a) 35 to 100% by weight textile smoothing agents according to the invention, b) 0 to 65% by weight Emulsifiers, antistatic agents and / or wetting agents c) 0 to 10% by weight pH regulators, bactericides and / or anti-corrosion agents, the amounts being chosen so that they add up to 100% by weight.
  • PETP pentaerythritol tetrapelargonate

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

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft thermostabile textile Glättemittel auf Basis von Polyolfettsäureester, wobei zur Erhöhung der Thermostabilität geringe Mengen an speziellen Estern von Thiocarbonsäuren eingetragen werden. Zudem betrifft die vorliegende Erfindung Spinnpräparationen, die diese textilen Glättemittel enthalten sowie ein Verfahren zur Herstellung der thermostabilen textilen Glättemittel.The invention relates to thermostable textile smoothing agents based on Polyol fatty acid esters, with small amounts to increase the thermal stability on special esters of thiocarboxylic acids. In addition The present invention relates to spin finishes using this textile Contain smoothing agents as well as a method for producing the thermostable textile smoothing agent.

Stand der TechnikState of the art

Bei der Herstellung und Verarbeitung synthetischer Fasern werden Spinnpräparationen eingesetzt. Diese Spinnpräparationen enthalten alle sogenannte textile Glättemittel, um Reibungen zwischen Filamenten bzw. Fasern und zwischen Filamenten und Führungsorganen herabzusetzen. Als textile Glättemittel werden in zunehmendem Maße Polyolcarbonsäureester eingesetzt. Die zunehmende Automatisierung der Fertigungsprozesse hat dazu geführt, daß an die textilen Glättemittel extrem hohe Anforderungen in Bezug auf ihre thermische Stabilität (Thermostabilität) gestellt werden. Diesen hohen Anforderungen können selbst die als thermisch stabil bekannten Polyolcarbonsäureester ohne weitere Zusätze kaum mehr in ausreichendem Maße entsprechen. In the manufacture and processing of synthetic fibers, spin finishes are used used. These spin finishes all contain so-called textile smoothing agent to avoid friction between filaments or fibers and to minimize between filaments and governing bodies. As a textile Smoothing agents are increasingly being used in polyol carboxylic acid esters. The increasing automation of manufacturing processes has led to that the textile smoothing agents have extremely high requirements in terms of their thermal stability (thermal stability) are provided. This high Even the polyol carboxylic acid esters known as thermally stable can meet requirements can hardly correspond sufficiently without additional additives.

Es ist daher vorgeschlagen worden, Antioxidantien wie butyliertes Hydroxytoluol (BHT) einzusetzen, weil derartige Verbindungen bereits in geringen bis mittleren Mengen die Thermostabilität wirksam verbessern. Unglücklicherweise haben BHT und verwandte Antioxidantien bei den Temperaturen, die bei der Herstellung und Verarbeitung textiler Fasern auftreten, eine relativ hohe Flüchtigkeit. Dies führt dazu, daß diese Klasse von Antioxidantien sich rasch verflüchtigt und daher seinen Zweck, eine oxidative Schädigung des textilen Glättemittels zu verhindern, nur anfänglich, aber nicht für den gesamten Prozeß erfüllen kann.It has therefore been suggested to use antioxidants such as butylated hydroxytoluene (BHT) to use because such connections are already in small up to medium quantities effectively improve the thermal stability. Unfortunately have BHT and related antioxidants at temperatures, that occur in the manufacture and processing of textile fibers, a relatively high volatility. This leads to this class of antioxidants quickly evaporates and therefore its purpose is an oxidative To prevent damage to the textile smoothing agent, only initially, however cannot meet for the whole process.

Es ist weiter vorgeschlagen worden, sterisch gehinderte Phenole als Antioxidantien, z. B. das dem Fachmann bekannte handelsübliche IrganoxR 1010, deren Flüchtigkeit relativ gering ist, einzusetzen. Dieses Vorgehen ist jedoch mit dem Nachteil verbunden, daß diese Gruppe von Antioxidantien nur eine begrenzte Löslichkeit in den Estern aufweist. Daraus ergibt sich, daß die erforderliche Konzentration an gelöstem Antioxidans nicht in ausreichendem Maße erreicht werden kann.It has also been proposed to use sterically hindered phenols as antioxidants, e.g. B. the commercially known Irganox R 1010 known to those skilled in the art, the volatility of which is relatively low. However, this procedure has the disadvantage that this group of antioxidants has only a limited solubility in the esters. It follows from this that the required concentration of dissolved antioxidant cannot be achieved to a sufficient extent.

Aus WO-A-9113134 ist ein Verfahren zur Verbesserung der Löslichkeit von Antioxidantien in Glättemitteln bekannt, wobei das Antioxidans über kovalente Bindungen in ein Trägermedium eingebaut wird. Die Lehre der WO 91/13134 bezieht sich dabei in ihrer bevorzugten Ausführungsform darauf, daß sogenannte "superstable lubricants" dann erhalten werden, wenn der Anteil des kovalenten gebundenen Antioxidans in dem Trägermedium im Bereich von größer 0 bis 30 Gew.-% liegt. In den Ausführungsbeispielen beträgt der Anteil des kovalent gebundenen Antioxidans in dem Trägermedium jeweils 10 bzw. 20 Gew.-%. Als Beispiel für ein besonders geeignetes Produkt wird ein textiles Glättemittel genannt, bei dem 10 Gew.-% IrganoxR 1010 mit Pentaerythritpelargonat als Träger kovalent verbunden ist. Aus ökonomischer und ökologischer Sicht ist es jedoch wünschenswert, den Gehalt an Antioxidantien zu minimieren. WO-A-9113134 discloses a method for improving the solubility of antioxidants in smoothing agents, the antioxidant being incorporated into a carrier medium via covalent bonds. The teaching of WO 91/13134 in its preferred embodiment relates to the fact that so-called "superstable lubricants" are obtained when the proportion of the covalently bound antioxidant in the carrier medium is in the range from greater than 0 to 30% by weight. In the exemplary embodiments, the proportion of the covalently bound antioxidant in the carrier medium is in each case 10 or 20% by weight. An example of a particularly suitable product is a textile smoothing agent in which 10% by weight of Irganox R 1010 is covalently bonded to pentaerythritol pelargonate as the carrier. From an economic and ecological point of view, however, it is desirable to minimize the antioxidant content.

Beschreibung der ErfindungDescription of the invention

Aufgabe der vorliegenden Erfindung war es, thermostabile textile Glättemittel bereitzustellen, die die genannten Nachteile des bekannten Standes der Technik vermeiden. Insbesondere war angestrebt, thermostabile textile Glättemittel zu entwickeln, die einen nur minimalen Anteil an Antioxidantien benötigen.The object of the present invention was to provide thermostable textile smoothing agents To provide the disadvantages of the known prior art avoid technology. In particular, the aim was to create thermostable textiles Developing smoothing agents that contain a minimal amount of antioxidants need.

Diese Aufgabe wurde erfindungsgemäß gelöst durch Glättemittel auf Basis von Polyolfettsäureester, denen zur Erhöhung der Thermostabilität Ester von Thiocarbonsäuren der allgemeinen Formel (I) und/oder (II) R1 - S - R2 - COOH HOOC - R3- S - R4- COOH worin R1 einen einwertigen Rest und R2, R3, R4 gleiche oder verschiedene zweiwertige Reste von Alkanen, Cycloalkanen, Aromaten oder Alkylaromaten mit 1 bis 22 C-Atomen bedeuten, eingetragen worden sind.This object was achieved according to the invention by smoothing agents based on polyol fatty acid esters, to which esters of thiocarboxylic acids of the general formula (I) and / or (II) are used to increase the thermal stability. R 1 - S - R 2 - COOH HOOC - R 3 - S - R 4 - COOH wherein R 1 is a monovalent radical and R 2 , R 3 , R 4 are identical or different divalent radicals of alkanes, cycloalkanes, aromatics or alkyl aromatics having 1 to 22 carbon atoms have been entered.

Der erste Gegenstand der vorliegenden Erfindung sind daher thermostabile textile Glättemittel, geeignet für Spinnpräparationen, auf Basis von Polyolfettsäureester, dadurch gekennzeichnet, daß zur Erhöhung der Thermostabilität in Mengen von 0,05 bis 8 Gew.-% - bezogen auf Polyolfettsäureester -The first object of the present invention are therefore thermostable textile smoothing agent, suitable for spin finishes, based on polyol fatty acid ester, characterized in that to increase the thermal stability in amounts of 0.05 to 8% by weight, based on polyol fatty acid esters

Ester der Thiocarbonsäuren der allgemeinen Formel (I) und/oder (II) R1 - S - R2 - COOH HOOC - R3- S - R4- COOH worin R1 einen einwertigen Rest und R2, R3, R4 gleiche oder verschiedene zweiwertige Reste von Alkanen, Cycloalkanen, Aromaten oder Alkylaromaten mit 1 bis 22 C-Atomen bedeuten, eingetragen worden sind.Esters of thiocarboxylic acids of the general formula (I) and / or (II) R 1 - S - R 2 - COOH HOOC - R 3 - S - R 4 - COOH wherein R 1 is a monovalent radical and R 2 , R 3 , R 4 are identical or different divalent radicals of alkanes, cycloalkanes, aromatics or alkyl aromatics having 1 to 22 carbon atoms have been entered.

Die Polyole sowie die Fettsäuren der Polyolfettsäureester können gesättigt oder olefinisch ungesättigt und in Bezug auf ihr Kohlenstoffgerüst geradkettig oder verzweigt sein.The polyols and the fatty acids of the polyol fatty acid esters can be saturated or olefinically unsaturated and straight-chain with respect to their carbon skeleton or be branched.

Die Reste R1 bis R4 können gesättigt oder olefinisch ungesättigt, geradkettig oder verzweigt sein, insoweit als es sich dabei um eine Alkyl-, Alkylen-, Cycloalkylen- oder Cycloalkylgruppe bzw. den Alkylteil einer Alkarylgruppe handelt.The radicals R 1 to R 4 can be saturated or olefinically unsaturated, straight-chain or branched, insofar as this is an alkyl, alkylene, cycloalkylene or cycloalkyl group or the alkyl part of an alkaryl group.

Unter Polyolen werden im Rahmen der vorliegenden Erfindung mehrwertige Alkohole mit mindestens 2 OH-Gruppen verstanden. Die chemische Konstitution der Polyole unterliegt dabei an sich keinen besonderen Beschränkungen, d.h. sie können geradkettig oder auch verzweigt sein. Bevorzugt sind die Polyole ausgewählt aus der von Glycerin, Trimethylolpropan, Neopentylglykol und Pentaerythrit gebildeten Gruppe.Polyols are polyvalent in the context of the present invention Alcohols understood with at least 2 OH groups. The chemical constitution the polyols are not subject to any particular restrictions, i.e. they can be straight or branched. Are preferred the polyols selected from that of glycerol, trimethylolpropane, neopentyl glycol and pentaerythritol formed group.

Die Fettsäurereste der Polyolfettsäureester leiten sich bevorzugt von Fettsäuren mit 8 bis 18 C-Atomen ab, die zudem vorzugsweise gesättigt sind. Die besten Effekte werden im Rahmen der vorliegenden Erfindung dann erzielt, wenn als Fettsäuren solche mit 8 bis 10 C-Atomen eingesetzt werden. Die letztgenannten Säuren sind dem Fachmann als Caprylsäure, Pelargonsäure und/oder Caprinsäure bekannt. Diese Säuren können entweder einzeln oder in Mischungen eingesetzt werden. Dabei sind Mischungen von C8- und C10-Fettsäure als sogenannte Vorlauf-Fettsäuren bekannt.The fatty acid residues of the polyol fatty acid esters are preferably derived from fatty acids with 8 to 18 carbon atoms, which are also preferably saturated. The best effects are achieved in the context of the present invention if those with 8 to 10 carbon atoms are used as fatty acids. The latter acids are known to those skilled in the art as caprylic acid, pelargonic acid and / or capric acid. These acids can be used either individually or in mixtures. Mixtures of C 8 and C 10 fatty acids are known as so-called pre-fatty acids.

Von den Estern der Thiocarbonsäuren sind diejenigen bevorzugt, bei denen die Thiocarbonsäuren der allgemeinen Formel (I) und/oder (II) mit monofunktionellen aliphatischen Alkoholen mit 1 bis 22 C-Atomen, Neopentylglykol, Glycerin, Trimethylolpropan oder Pentaerythrit verestert sind. Bei den mehrfunktionellen Alkoholen Neopentylglykol, Glycerin, Trimethylolpropan und Pentaerythrit kann es sich um reine oder aber auch um gemischte Ester handeln. Unter "reinen" Estern werden solche Ester verstanden, in denen alle Hydroxylgruppen der mehrfunktionellen Alkohole mit einer oder mehreren Thiocarbonsäuren der allgemeinen Formel (I) und/oder (II) verestert sind. Unter "gemischten" Estern werden solche Ester verstanden, in denen wenigstens eine Hydroxylgruppe mit einer Thiocarbonsäure der allgemeinen Formel (I) oder (II) verestert ist. Die anderen Hydroxylgruppen sind dann mit Fettsäuren mit 6 bis 22 C-Atomen, wie sie im Zusammenhang mit den Polyolfettsäureestern beschrieben sind, verestert. Besonders bevorzugt werden die Ester von monofunktionellen aliphatischen Alkoholen der beschriebenen Art und die "reinen" Ester des Pentaerythrits. Bei den monofunktionellen aliphatischen Alkoholen eignen sich insbesondere n- und i-Butanol, 2-Ethylhexanol, Isotridecylalkohol, Laurylalkohol, Isostearylalkohol und/oder Oleylalkohol.Of the esters of thiocarboxylic acids, those are preferred in which the thiocarboxylic acids of the general formula (I) and / or (II) with monofunctional aliphatic alcohols with 1 to 22 carbon atoms, neopentyl glycol, Glycerin, trimethylolpropane or pentaerythritol are esterified. At the polyfunctional alcohols neopentyl glycol, glycerin, trimethylol propane and pentaerythritol can be pure or mixed Trade esters. "Pure" esters are understood to mean such esters, in which all hydroxyl groups of the polyfunctional alcohols with one or esterified several thiocarboxylic acids of the general formula (I) and / or (II) are. "Mixed" esters are understood to mean those esters in which have at least one hydroxyl group with a thiocarboxylic acid of the general Formula (I) or (II) is esterified. The other hydroxyl groups are then related to fatty acids with 6 to 22 carbon atoms as they are are described with the polyol fatty acid esters. Particularly preferred are the esters of monofunctional aliphatic alcohols described type and the "pure" esters of pentaerythritol. With the monofunctional aliphatic alcohols are particularly suitable for n- and i-butanol, 2-ethylhexanol, isotridecyl alcohol, lauryl alcohol, isostearyl alcohol and / or oleyl alcohol.

Unter den Thiocarbonsäuren der allgemeinen Formel (I) werden solche bevorzugt, in der R1 eine Alkylgruppe mit 6 bis 18 C- Atomen und R2 eine Alkylengruppe mit 1 oder 2 C-Atomen bedeutet. Besonders geeignete Beispiele sind β-Laurylthiopropionsäure (C12H25SCH2CH2COOH) und β-Octylthiopropionsäure (C8H17SCH2CH2COOH).Among the thiocarboxylic acids of the general formula (I), preference is given to those in which R 1 denotes an alkyl group with 6 to 18 C atoms and R 2 denotes an alkylene group with 1 or 2 C atoms. Particularly suitable examples are β-laurylthiopropionic acid (C 12 H 25 SCH 2 CH 2 COOH) and β-octylthiopropionic acid (C 8 H 17 SCH 2 CH 2 COOH).

Unter den Thiocarbonsäuren der allgemeinen Formel (II) werden solche bevorzugt, in der R3 und R4 eine Alkylengruppe mit 2 C-Atomen bedeutet, d.h. die Thiodipropionsäure (HOOCCH2CH2SCH2CH2COOH).Among the thiocarboxylic acids of the general formula (II), preference is given to those in which R 3 and R 4 are an alkylene group having 2 carbon atoms, ie thiodipropionic acid (HOOCCH 2 CH 2 SCH 2 CH 2 COOH).

Die Ester der Thiocarbonsäure sind im Handel erhältliche Verbindungen, die aber auch einfach durch bekannte Veresterungsreaktionen zugänglich sind. The esters of thiocarboxylic acid are commercially available compounds that but are also easily accessible by known esterification reactions.

Die gemischten Ester kann man leicht durch Umesterung der reinen Thiosäureester mit den beschriebenen Fettsäuren erhalten.The mixed esters can easily be obtained by transesterification of the pure thioates obtained with the fatty acids described.

Bei der Herstellung der erfindungsgemäßen thermostabilen textilen Glättemittel werden die Ester der Thiocarbonsäuren in einer Menge von 0,05 bis 8 Gew.-% - bezogen auf die Polyolfettsäureester - eingesetzt. Dabei ist es bevorzugt, die Ester der Thiocarbonsäuren in einer Menge von 0,5 bis 5 Gew.-%, insbesondere von 1,0 bis 3,0 Gew.-%, einzusetzen. Diese Angabe der eingesetzten Mengen beziehen sich auf die oben definierten Mengen an reinen Estern der Thiocarbonsäuren. Bei gemischten Estern der Thiocarbonsäuren sind entsprechend dem Gehalt an Thiocarbonsäuren im Ester höhere Mengen einzusetzen. Die Ester der Thiocarbonsäuren werden in die Polyolfettsäureester eingetragen. Nach einer Ausführungsform der vorliegenden Erfindung werden die Ester der Thiocarbonsäuren in die Polyolfettsäureester bei Temperaturen von 20 bis 80 °C eingerührt. Dabei können in die vorgelegten, erwärmten Polyolfettsäureester die Ester der Thiocarbonsäuren eingerührt werden oder man gibt die Ester der Thiocarbonsäuren zu den Polyolfettsäureester und erwärmt unter Rühren. Nach einer zweiten und bevorzugten Ausführungsform werden die Polyolfettsäureester mit den Estern der Thiocarbonsäuren der allgemeinen Formel (I) und/oder (II) bei Temperaturen von 90 bis 170 °C in Anwesenheit eines Umesterungskatalysators umgesetzt. Als Umesterungskatalysatoren eignen sich Verbindungen auf Zinnbasis wie Zinnoctoat sowie Natriummethylat. Die Umesterungskatalysatoren sind in einer Menge von 0,01 bis 2 Gew.% - bezogen auf die gesamte Menge an Polyolfettsäureester und Ester der Thiocarbonsäuren - zugegen.In the manufacture of the thermostable textile smoothing agents according to the invention are the esters of thiocarboxylic acids in an amount of 0.05 to 8 % By weight - based on the polyol fatty acid esters. It is preferred, the esters of thiocarboxylic acids in an amount of 0.5 to 5 % By weight, in particular from 1.0 to 3.0% by weight, to be used. This indication of Amounts used relate to the amounts defined above pure esters of thiocarboxylic acids. With mixed esters of thiocarboxylic acids are higher according to the content of thiocarboxylic acids in the ester Use quantities. The esters of thiocarboxylic acids are converted into the polyol fatty acid esters registered. According to one embodiment of the present Invention are the esters of thiocarboxylic acids in the polyol fatty acid esters stirred in at temperatures of 20 to 80 ° C. You can in the submitted, heated polyol fatty acid esters of thiocarboxylic acids are stirred in or the esters of thiocarboxylic acids are added to the polyol fatty acid esters and heated with stirring. After a second and preferred Embodiment are the polyol fatty acid esters with the esters Thiocarboxylic acids of general formula (I) and / or (II) at temperatures from 90 to 170 ° C in the presence of a transesterification catalyst. Tin-based compounds such as are suitable as transesterification catalysts Tin octoate and sodium methylate. The transesterification catalysts are in an amount of 0.01 to 2 wt.% - Based on the total amount of polyol fatty acid ester and esters of thiocarboxylic acids.

Gemäß einer weiteren und insbesondere bevorzugten Ausführungsform der vorliegenden Erfindung werden den erfindungsgemäßen Glättemitteln zusätzlich Antioxidantien als Additiv zugegeben. Diese Antioxidantien werden mit oder nach dem Eintrag der Ester der Thiocarbonsäuren, der vorzugsweise bei Temperaturen von 90 bis 170 °C in Gegenwart der Umesterungskatalysatoren erfolgt, zugegeben. Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung von thermostabilen textilen Glättemitteln auf Basis von Polyolfettsäureestern, dadurch gekennzeichnet, daß die Polyolfettsäureester mit 0,05 bis 8 Gew.% - bezogen auf Polyolfettsäureester - an Estern der Thiocarbonsäuren der allgemeinen Formel (I) und/oder (II) R1 - S - R2 - COOH HOOC - R3- S - R4- COOH worin R1 einen einwertigen Rest und R2, R3, R4 gleiche oder verschiedene zweiwertige Reste von Alkanen, Cycloalkanen, Aromaten oder Alkylaromaten mit 1 bis 22 C-Atomen bedeuten.
bei Temperaturen von 90 bis 170 °C in Anwesenheit eines Umesterungskatalysators umgesetzt werden, ggf. in Anwesenheit zusätzlicher Antioxidantien. Die zusätzlichen Antioxidantien können von Anfang an bei dem Verfahren zugegen sein oder während des Verfahrens zugegeben werden oder aber auch nachträglich zugesetzt werden.According to a further and particularly preferred embodiment of the present invention, antioxidants are additionally added as an additive to the smoothing agents according to the invention. These antioxidants are added with or after the entry of the esters of thiocarboxylic acids, which is preferably carried out at temperatures from 90 to 170 ° C. in the presence of the transesterification catalysts. Another object of the present invention is therefore a process for the preparation of thermostable textile smoothing agents based on polyol fatty acid esters, characterized in that the polyol fatty acid esters with 0.05 to 8 wt.% - Based on polyol fatty acid esters - on esters of thiocarboxylic acids of the general formula (I ) and / or (II) R 1 - S - R 2 - COOH HOOC - R 3 - S - R 4 - COOH wherein R 1 is a monovalent radical and R 2 , R 3 , R 4 are identical or different divalent radicals of alkanes, cycloalkanes, aromatics or alkyl aromatics having 1 to 22 carbon atoms.
at temperatures of 90 to 170 ° C in the presence of a transesterification catalyst, optionally in the presence of additional antioxidants. The additional antioxidants can be present in the process from the beginning or can be added during the process or can also be added subsequently.

Als Antioxidantien eignen sich butyliertes Hydroxytoluol, Dialkyl- oder Diarylphosphonate, Trialkyl- oder Triarylphosphite, Ascorbin- oder Zitronensäure und deren Derivate und in besonderem Maße sterisch gehinderte Phenole.Suitable antioxidants are butylated hydroxytoluene, dialkyl or Diaryl phosphonates, trialkyl or triaryl phosphites, ascorbic or citric acid and their derivatives and especially sterically hindered Phenols.

Als spezielle Beispiele für erfindungsgemäß geeignete sterisch gehinderte Phenole seien die nachstehend aufgeführten Verbindungen A-1 bis A-6 genannt.

Figure 00080001
Figure 00090001
Figure 00090002
Figure 00090003
Figure 00100001
Figure 00100002
Compounds A-1 to A-6 listed below may be mentioned as specific examples of sterically hindered phenols suitable according to the invention.
Figure 00080001
Figure 00090001
Figure 00090002
Figure 00090003
Figure 00100001
Figure 00100002

Besonders bevorzugt werden als zusätzliche Additive die sterisch gehinderten Phenole der Struktur (A-1 und/oder A-6) eingesetzt.The sterically hindered are particularly preferred as additional additives Phenols of the structure (A-1 and / or A-6) used.

Durch die zusätzlichen Additive wird erreicht, daß die an sich schon gute Thermostabilität der erfindungsgemäßen textilen Glättemittel in synergistischer Weise weiter verbessert wird. Dies ist unter anderem daran zu erKennen, daß wesentlich geringere Mengen an den Antioxidantien zugesetzt werden müssen als beispielsweise in der WO 91/13134 (10 bis 20 Gew.%) beschrieben, um vergleichbare Thermostabilitäten zu erreichen. So ergeben beispielsweise schon Mengen von 1,0 Gew.% an dem sterisch gehinderten Phenol IrganoxR 1010 - bezogen auf die gesamte Menge an Polyolfettsäureester und Ester der Thiocarbonsäuren - hervorragende Thermostabilitäten.The additional additives ensure that the inherently good thermal stability of the textile smoothing agents according to the invention is further improved in a synergistic manner. This can be seen, inter alia, from the fact that much smaller amounts of the antioxidants have to be added than described, for example, in WO 91/13134 (10 to 20% by weight) in order to achieve comparable thermostabilities. For example, even amounts of 1.0% by weight of the sterically hindered Irganox R 1010 phenol - based on the total amount of polyol fatty acid ester and ester of thiocarboxylic acids - result in excellent thermostabilities.

Generell gesehen, empfiehlt es sich im Sinne der Erfindung, die Antioxidantien im Verhältnis zu den Estern der Thiocarbonsäuren in einer Menge von 1:1 bis 1:4 zuzugeben. Dabei werden bei den sterisch gehinderten Phenolen besonders gute Ergebnisse erzielt, wenn die Menge der zusätzlichen Antioxidantien d) 10 bis 50 Gew.% - bezogen auf die Ester der Thiocarbonsäuren - beträgt, wobei der Bereich von 20 bis 30 Gew.-% besonders bevorzugt ist.Generally speaking, it is recommended in the sense of the invention, the antioxidants in relation to the esters of thiocarboxylic acids in an amount of Add 1: 1 to 1: 4. The sterically hindered phenols Particularly good results are obtained when the amount of additional antioxidants d) 10 to 50% by weight, based on the esters of thiocarboxylic acids , the range from 20 to 30% by weight being particularly preferred.

Die erfindungsgemäßen textilen Glättemittel, mit und ohne zusätzliche Antioxidantien, können aufgrund ihrer hohen Thermostabilität unter anderem in Spinnpräparationen verwendet werden. Ein weiterer Gegenstand der vorliegenden Erfindung sind daher Spinnpräparationen für synthetische Filamente, dadurch gekennzeichnet, daß sie die beschriebenen thermostabilen textilen Glättemittel enthalten. Wobei die textilen Glättemittel wiederum die zusätzlichen Antioxidantien enthalten können. Die Spinnpräparationen enthalten dabei mindestens zu etwa 35 Gew.% die textilen Glättemittel. Weitere Bestandteile der Spinnpräparationen können Emulgatoren, Netzmittel und/oder Antistatika sowie die aus dem Stand der Technik bekannten Hilfsmittel wie Fadenschlußmittel, pH-Wert- Regulatoren, Bakterizide und/oder Korrosionsschutzmittel sein.The textile smoothing agents according to the invention, with and without additional antioxidants, can because of their high thermal stability among other things can be used in spin finishes. Another subject of the present Invention are therefore spin finishes for synthetic filaments, characterized in that they have the described thermostable contain textile smoothing agents. The textile smoothing agent in turn which may contain additional antioxidants. The spin finishes contain at least about 35% by weight of the textile smoothing agents. Other components of the spin finishes can be emulsifiers, wetting agents and / or antistatic agents and the auxiliaries known from the prior art such as thread closing agents, pH regulators, bactericides and / or Be anti-corrosion agent.

Als Emulgatoren, Netzmittel und/oder Antistatika kommen anionische, kationische und/oder nichtionische Tenside in Betracht, wie Mono- und/oder Diglyceride, beispielsweise Glycerinmono- und/oder Glycerindioleat, alkoxylierte, vorzugsweise ethoxylierte und/oder propoxylierte Fette bzw. Öle, Fettalkohole mit 8 bis 24 C-Atomen und/oder C8-18-Alkylphenole, beispielsweise Anlagerungsprodukte von 25 mol Ethylenoxid an Rizinusöl und/oder Anlagerungsprodukte von 8 mol Propylenoxid und 6 Mol Ethylenoxid an C16-18-Fettalkohole, gewünschtenfalls alkoxylierte C8-24-Fettsäuremono- und/oder Diethanolamide, beispielsweise - gegebenenfalls ethoxyliertes - Ölsäuremono- und/oder -diethanolamid, Talgfettsäuremono- und/oder -diethanolamid und/oder Kokosfettsäuremono- und/oder -diethanolamid, Alkali- und/oder Ammoniumsalze alkoxylierter, vorzugsweise ethoxylierter und/oder propoxylierter, gegebenenfalls endgruppenverschlossener C8-22-Alkyl- und/oder C8-22-Alkylenalkoholsulfonate, Umsetzungsprodukte aus gegebenenfalls alkoxylierten C8-22-Alkylalkoholen mit Phosphorpentoxid oder Phosphoroxychlorid in Form ihrer Alkali-, Ammonium- und/oder Aminsalze, beispielsweise Phosphorsäureester von ethoxylierten C12-14-Fettalkoholen, neutralisiert mit Alkanolamin, Alkali- und/oder Ammoniumsalze von C8-22-Alkylsulfosuccinaten, beispielsweise Natriumdioctylsulfosuccinat und/oder Aminoxiden, beispielsweise Dimethyldodecylaminoxid. Bei dieser beispielhaften Aufzählung ist zu berücksichtigen, daß eine Vielzahl der genannten Substanzen nicht nur eine Funktion, sondern auch mehrere Funktionen besitzen können; so kann ein Antistatikum etwa gleichzeitig als Emulgator wirken.Suitable emulsifiers, wetting agents and / or antistatic agents are anionic, cationic and / or nonionic surfactants, such as mono- and / or diglycerides, for example glycerol mono- and / or glycerol dioleate, alkoxylated, preferably ethoxylated and / or propoxylated fats or oils, fatty alcohols with 8 to 24 carbon atoms and / or C 8-18 alkylphenols, for example addition products of 25 mol ethylene oxide onto castor oil and / or addition products of 8 mol propylene oxide and 6 mol ethylene oxide onto C 16-18 fatty alcohols, if desired alkoxylated C 8- 24 fatty acid mono- and / or diethanolamides, for example - optionally ethoxylated - oleic acid mono- and / or diethanolamide, tallow fatty acid mono- and / or diethanolamide and / or coconut fatty acid mono- and / or diethanolamide, alkali and / or ammonium salts of alkoxylated, preferably ethoxylated and / or propoxylated, optionally end-capped C 8-22 alkyl and / or C 8-22 alkylene alcohol sulfonates, reaction Products from optionally alkoxylated C 8-22 alkyl alcohols with phosphorus pentoxide or phosphorus oxychloride in the form of their alkali, ammonium and / or amine salts, for example phosphoric acid esters of ethoxylated C 12-14 fatty alcohols, neutralized with alkanolamine, alkali and / or ammonium salts of C. 8-22 alkyl sulfosuccinates, for example sodium dioctyl sulfosuccinate and / or amine oxides, for example dimethyldodecylamine oxide. In this exemplary enumeration it must be taken into account that a large number of the substances mentioned can have not only one function but also several functions; an antistatic can act as an emulsifier at about the same time.

Weitere fakultative Bestandteile können die üblichen Hilfsstoffe sein. Als Fadenschlußmittel sind die aus dem Stand der Technik bekannten Polyacrylate, Fettsäuresarcoside und/oder Mischpolymerisate mit Maleinsäureanhydrid geeignet. Geeignete pH-Wert-Regulatoren sind C1-4-Carbonsäuren und/oder C1-4-Hydroxycarbonsäuren, z. B. Essigsäure und/oder Glykolsäure, Alkalihydroxide wie Kaliumhydroxid und/oder Amine wie Triethanolamid, auch die Anwesenheit von Bakteriziden und/oder Korrosionsschutzmittel ist möglich.Other optional ingredients can be the usual auxiliary substances. Suitable thread closure agents are the polyacrylates, fatty acid sarcosides and / or copolymers with maleic anhydride known from the prior art. Suitable pH regulators are C 1-4 carboxylic acids and / or C 1-4 hydroxycarboxylic acids, e.g. B. acetic acid and / or glycolic acid, alkali hydroxides such as potassium hydroxide and / or amines such as triethanolamide, the presence of bactericides and / or anti-corrosion agents is possible.

Die erfindungsgemäßen Spinnpräparationen lassen sich durch intensives Vermischen der erfindungsgemäßen textilen Glättemittel ggf. mit den Emulgatoren, Netzmittel, Antistatika und ggf. mit den üblichen Hilfsstoffen bei ca. 18-25 °C herstellen.The spin finishes according to the invention can be mixed intensively the textile smoothing agent according to the invention, optionally with the emulsifiers, Wetting agents, antistatic agents and, if necessary, with the usual additives Produce approx. 18-25 ° C.

Wie in der Textilindustrie üblich, werden die Spinnpräparationen in Form ihrer wäßrigen Dispersionen auf die synthetischen Filamentfasern unmittelbar nach Austritt aus der Spinndüse appliziert. Die Spinnpräparationen, die eine Temperatur zwischen 18 und 60 °C haben, werden dabei mit Hilfe von Auftragswalzen oder Dosierpunkten über geeignete Applikatoren aufgebracht. Bevorzugt werden Spinnpräparationen in Form ihrer wäßrigen Dispersion, die einen Gesamtaktivsubstanzgehalt zwischen etwa 3 und 40 Gew.-%, vorzugsweise zwischen 5 und 30 Gew.-%, aufweisen. Bezogen auf den Gesamtaktivsubstanzgehalt enthalten dabei die erfindungsgemäßen Spinnpräparationen a) 35 bis 100 Gew.-% erfindungsgemäße textile Glättemittel, b) 0 bis 65 Gew.-% Emulgatoren, Antistatika und/oder Netzmittel c) 0 bis 10 Gew.-% pH-Wert-Regulatoren, Bakterizide und/oder Korrosionsschutzmittel, wobei die Mengen so gewählt werden, daß sie sich zu 100 Gew.-% addieren. As is common in the textile industry, the spin finishes are applied in the form of their aqueous dispersions to the synthetic filament fibers immediately after exiting the spinneret. The spin finishes, which have a temperature between 18 and 60 ° C, are applied with the help of application rollers or dosing points using suitable applicators. Preference is given to spin finishes in the form of their aqueous dispersion which have a total active substance content of between about 3 and 40% by weight, preferably between 5 and 30% by weight. Based on the total active substance content, the spin finishes according to the invention contain a) 35 to 100% by weight textile smoothing agents according to the invention, b) 0 to 65% by weight Emulsifiers, antistatic agents and / or wetting agents c) 0 to 10% by weight pH regulators, bactericides and / or anti-corrosion agents, the amounts being chosen so that they add up to 100% by weight.

BeispieleExamples 1. Pentaerythrittetrapelargonat (PETP) und 5 Gew.-% Pentaerythrittetrakisoctylthiopropionat1. pentaerythritol tetrapelargonate (PETP) and 5% by weight pentaerythritol tetrakisoctylthiopropionate

In einem Dreihalskolben versehen mit Rührer, Rückflußkühler und Stickstoffzuleitung wurden 1330 g PETP und 70 g Pentaerythrittetrakisoctylthiopropionat auf 90 °C erhitzt. Anschließend wurden 3,5 g 25 gew.-%ige Natriummethylat-Lösung zugegeben und bei 90 bis 100 °C etwa 1 Stunde lang gerührt, bevor phosphorige Säure zur Neutralisation zugegeben worden ist. Man erhielt eine blaßgelbe Flüssigkeit. Zur Aufarbeitung wurde das Produkt mit Wasser bis zum pH-Wert des Waschwassers von 7,1-7,3 gewaschen, getrocknet und gebleicht.In a three-necked flask equipped with a stirrer, reflux condenser and nitrogen feed 1330 g PETP and 70 g pentaerythritol tetrakisoctylthiopropionate heated to 90 ° C. Then 3.5 g of 25 wt .-% sodium methylate solution added and stirred at 90 to 100 ° C for about 1 hour, before phosphorous acid has been added for neutralization. You got a pale yellow liquid. The product was processed with Washed water until the pH of the wash water is 7.1-7.3, dried and bleached.

2. PETP und 4 Gew.-% Pentaerythrittetrakisoctylthiopropionat und 1 Gew.-% IrganoxR 10102. PETP and 4% by weight pentaerythritol tetrakisoctylthiopropionate and 1% by weight Irganox R 1010

Es wurde analog 1. gearbeitet, jedoch mit 56 g Pentaerythrittetrakisoctylthiopropionat und 14 g IrganoxR 1010.The procedure was analogous to 1st, but with 56 g of pentaerythritol tetrakisoctylthiopropionate and 14 g of Irganox R 1010.

3. PETP und 2 Gew.-% Diisotridecylthiodipropionat und 1 Gew.-% IrganoxR 10103. PETP and 2% by weight diisotridecylthiodipropionate and 1% by weight Irganox R 1010

Es wurde analog 1. gearbeitet, jedoch mit 1358 g PETP, 28 g Diisotridecylthiodipropionat und 14 g IrganoxR 1010.The procedure was analogous to 1, but with 1358 g PETP, 28 g diisotridecylthiodipropionate and 14 g Irganox R 1010.

Claims (13)

  1. Thermally stable textile lubricants suitable for spin finishes based on polyol fatty acid esters, characterized in that, to increase thermal stability,
    a) esters of thiocarboxylic acids corresponding to general formulae (I) and/or (II) R1-S-R2-COOH HOOC-R3-S-R4-COOH in which R1 is a monofunctional residue of alkanes, cycloalkanes, aromatics or alkyl aromatics containing 1 to 22 carbon atoms and R2, R3 and R4 may be the same or different and represent difunctional residues of alkanes, cycloalkanes, aromatics or alkyl aromatics containing 1 to 22 carbon atoms,
    are introduced into the polyol fatty acid esters in quantities of 0.05 to 8% by weight, based on polyol fatty acid ester
    or
    b) transesterification products of the esters of the thiocarboxylic acids corresponding to general formulae (I) and/or (II) are present with the polyol fatty acid esters in quantities of 0.05 to 8% by weight, based on polyol fatty acid ester.
  2. Lubricants as claimed in claim 1, characterized in that the polyols of the polyol fatty acid esters are selected from the group consisting of neopentyl glycol, glycerol, trimethylol propane and pentaerythritol.
  3. Lubricants as claimed in claim 1 or 2, characterized in that the fatty acids of the polyol fatty acid esters contain 8 to 18 carbon atoms and are preferably saturated.
  4. Lubricants as claimed in any of claims 1 to 3, characterized in that the fatty acids of the polyol fatty acid esters are caprylic acid, pelargonic acid and/or capric acid.
  5. Lubricants as claimed in any of claims 1 to 4, characterized in that the thiocarboxylic acids are esterified with monohydric aliphatic alcohols containing 1 to 22 carbon atoms, neopentyl glycol, glycerol, trimethylol propane or pentaerythritol.
  6. Lubricants as claimed in any of claims 1 to 5, characterized in that, in formula (I), R1 - is an alkyl group containing 6 to 18 carbon atoms and R2 is an alkylene group containing 1 or 2 carbon atoms.
  7. Lubricants as claimed in any of claims 1 to 6, characterized in that, in formula (II), R3 and R4 represent an alkylene group containing 2 carbon atoms.
  8. Lubricants as claimed in any of claims 1 to 7, characterized in that the thiocarboxylic acid esters are introduced in a quantity of 0.5 to 5% by weight and, more particularly, 1 to 3% by weight, based on the polyol fatty acid ester.
  9. Lubricants as claimed in any of claims 1 to 8, characterized in that the thiocarboxylic acid esters are stirred into the polyol fatty acid esters at temperatures of 20 to 80°C.
  10. Lubricants as claimed in any of claims 1 to 9, characterized in that the lubricants additionally contain antioxidants, preferably sterically hindered phenols.
  11. Lubricants as claimed in claim 10, characterized in that the antioxidants and the thiocarboxylic acid esters are used in a quantity ratio of 1:1 to 1:4.
  12. Spin finishes for synthetic filaments, characterized in that they contain the thermally stable textile lubricants claimed in claim 1.
  13. A process for the production of thermally stable textile lubricants based on polyol fatty acid esters, characterized in that the polyol fatty acid esters are reacted with 0.05 to 8 % by weight, based on polyol fatty acid ester, of esters of thiocarboxylic acids corresponding to general formula (I) and/or (II): R1 - S - R2 - COOH HOOC - R3 - S - R4 - COOH in which R1 represents a monofunctional residue of alkanes, cycloalkanes, aromatics or alkyl aromatics, and R2, R3 and R4 may be the same or different and represent an alkyl, cycloalkyl, aryl or alkaryl group containing 1 to 22 carbon atoms,
    ar temperatures of 90 to 170°C in the presence of a transesterification catalyst and optionally in the presence of additional antioxidants.
EP95921839A 1994-06-16 1995-06-07 Thermally stable textile smoothing agents Expired - Lifetime EP0765414B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US260854 1988-10-18
US08/260,854 US5478485A (en) 1994-06-16 1994-06-16 Thermally stable textile lubricants
PCT/EP1995/002190 WO1995034709A1 (en) 1994-06-16 1995-06-07 Thermally stable textile smoothing agents

Publications (2)

Publication Number Publication Date
EP0765414A1 EP0765414A1 (en) 1997-04-02
EP0765414B1 true EP0765414B1 (en) 1999-02-03

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EP95921839A Expired - Lifetime EP0765414B1 (en) 1994-06-16 1995-06-07 Thermally stable textile smoothing agents

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US (1) US5478485A (en)
EP (1) EP0765414B1 (en)
DE (1) DE59505043D1 (en)
ES (1) ES2128737T3 (en)
WO (1) WO1995034709A1 (en)

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US5856280A (en) * 1996-07-12 1999-01-05 Exxon Research And Engineering Company Sulfur-containing carboxylic acid derivatives to reduce deposit forming tendencies and improve antioxidancy of aviation turbine oils
WO1998024559A1 (en) * 1996-12-05 1998-06-11 Henkel Corporation Thioesters as boundary lubricants
EP0905301A1 (en) * 1997-09-02 1999-03-31 Chimitex S.A.R.L. Size for the low temperature sizing system
US6106942A (en) * 1998-12-02 2000-08-22 Celanese Acetate Llc Liquid crystalline polymer monofilaments having improved adhesion characteristics
DE10204808A1 (en) * 2002-02-06 2003-08-14 Cognis Deutschland Gmbh Use of ethoxylated fatty acids as a smoothing agent for synthetic and natural fibers
US20060054039A1 (en) * 2002-12-03 2006-03-16 Eliahu Kritchman Process of and apparratus for three-dimensional printing
CN107043455B (en) * 2016-12-30 2019-11-26 广州星业科技股份有限公司 A kind of polyvalent alcohol aliphatic ester and the preparation method and application thereof
JP6445205B1 (en) * 2018-06-28 2018-12-26 竹本油脂株式会社 Synthetic fiber treatment agent and synthetic fiber

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Also Published As

Publication number Publication date
WO1995034709A1 (en) 1995-12-21
EP0765414A1 (en) 1997-04-02
US5478485A (en) 1995-12-26
DE59505043D1 (en) 1999-03-18
ES2128737T3 (en) 1999-05-16

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