EP0765415B1 - Thermally stable textile smoothing agents - Google Patents

Description

Field of the Invention

The invention relates to thermostable textile smoothing agents obtainable by reacting polyols with C _6-22 fatty acids in the presence of small amounts of special esters of thiocarboxylic acids and spin finishes which contain these textile smoothing agents.

State of the art

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 esters. The increasing Automation of manufacturing processes has led to the textile Smoothing agents have extremely high requirements with regard to their thermal Stability (thermal stability) are provided. These high demands can even the esters known as thermally stable without further additives hardly correspond to a sufficient extent.

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, BHT and related antioxidants at temperatures, that occur in the manufacture and processing of textile fibers, a relatively high volatility. As a result, this class of Antioxidants evaporate quickly and therefore its purpose is an oxidative To prevent damage to the textile smoothing agent, only initially, but cannot satisfy the entire process.

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.

A method for improving the solubility of antioxidants in smoothing agents is known from WO 91/13134, 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 a carrier. From an economic and ecological point of view, however, it is desirable to minimize the antioxidant content.

GB-A-454 449 describes the use of certain carboxylic acids or thiocarboxylic acids as a replacement for oleic acid as spinning oil.

GB-A-738 749 describes a mixture of water-soluble alkali salt of an organic acid and water-insoluble fatty acid glycol ester or fatty alcohol ether as an additive in spin finishes to improve the emulsion properties.

GB-A-930 336 describes esters of polyols and fatty acids in a mixture with other constituents as spinning oils. Thiocarboxylic acid esters are not included.

Finally, GB-A-499 371 describes the addition of certain sulfur-containing compounds as antioxidants to smoothing agents which contain unsaturated compounds.

Description of the invention

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.

a) Polyolen mit

b) Fettsäuren mit 6 bis 22 C-Atomen

in Gegenwart von 0,05 bis 8 Gew.-% - bezogen auf die Summe der Komponenten a) und b) - an

c) Estern 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.This object was achieved according to the invention by smoothing agents which can be obtained by reacting

a) Polyols with

b) fatty acids with 6 to 22 carbon atoms

in the presence of 0.05 to 8% by weight, based on the sum of components a) and b)

c) 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.

The polyols a) and the fatty acids b) can be saturated or olefinic unsaturated and straight or branched with respect to their carbon skeleton be.

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. Are preferred the polyols selected from that of glycerol, trimethylolpropane, neopentyl glycol and pentaerythritol formed group.

With regard to component b), the fatty acids with 8 to 18 carbon atoms are preferred, which are also preferably saturated. The best effects are achieved in the context of the present invention if fatty acids with 8 to 10 carbon atoms are used as component b). The latter acids are known to those skilled in the art as caprylic acid, pelargonic acid and capric acid. These acids can be used as component b) either individually or in mixtures. Mixtures of C ₈ and C ₁₀ fatty acids are known as so-called pre-fatty acids.

With regard to component c), such esters of thiocarboxylic acids are preferred in which the thiocarboxylic acids of the general formula (I) and / or (II) with monofunctional aliphatic alcohols with 1 to 22 C atoms, neopentyl glycol, glycerin, trimethylolpropane or pentaerythritol are esterified. For the polyfunctional alcohols neopentyl glycol, glycerin, Trimethylolpropane and pentaerythritol can be pure or else also act as mixed esters. Such "esters" are called "pure" esters understood in which all hydroxyl groups of the polyfunctional alcohols with one or more thiocarboxylic acids of the general formula (I) and / or (II) are esterified. "Mixed" esters are such Understood esters in which at least one hydroxyl group with a Thiocarboxylic acid of the general formula (I) or (II) is esterified. The other hydroxyl groups are then with fatty acids with 6 to 22 carbon atoms, as described in connection with component b), esterified. The esters of monofunctional aliphatic are particularly preferred Alcohols of the type described and the "pure" esters of pentaerythritol. The monofunctional aliphatic alcohols are particularly suitable n- and i-butanol, 2-ethylhexanol, isotridecanol, lauryl alcohol, isostearyl alcohol and / or oleyl alcohol.

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).

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).

The 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.

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 sum of components a) and b), is used. It is preferred to use the esters of thiocarboxylic acids in an amount of 0.5 to 5 wt .-%, in particular from 1.0 to 3.0 wt .-%, use. This The quantities used relate to the quantities defined above on pure esters of thiocarboxylic acids. With mixed esters of thiocarboxylic acids are in accordance with the content of thiocarboxylic acids in the ester use higher quantities. The esters of thiocarboxylic acids can be used in the Implementation between polyols a) and fatty acids b) from the beginning be or be added only during the implementation. Furthermore they can be added in their entirety or in portions will. The reaction between polyols a) and the fatty acids b) takes place under the conditions customary for esterification reactions. The presence the esters of thiocarboxylic acids of the general formula (I) and / or (II) causes an improvement in thermal stability on the one hand and on the other a color improvement of the textile smoothing agents obtained, since these are lighter in color than when manufactured without the presence of those described Esters of thiocarboxylic acids.

In one embodiment of the present invention, the invention Agents additionally added antioxidants as additive d). This Antioxidants are added after the reaction of the polyols a) with fatty acids b) added in the presence of the esters of thiocarboxylic acids. As antioxidants butylated hydroxytoluene, dialkyl or diarylphosphonates are suitable, Trialkyl or triaryl phosphites, ascorbic or citric acid and their Derivatives and especially sterically hindered phenols.

Compounds A-1 to A-6 listed below may be mentioned as specific examples of sterically hindered phenols suitable according to the invention.

The sterically hindered are particularly preferred as additional additives Phenols of the structure (A-1 and / or A-6) used.

The additional additives d) 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 significantly smaller amounts of the antioxidants d) 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 components a) to c) - give excellent thermal stability.

Generally speaking, it is recommended in the sense of the invention, the antioxidants d) in relation to the esters of thiocarboxylic acids in an amount from 1: 1 to 1: 4. The sterically hindered phenols particularly good results if the amount of additional Antioxidants d) 10 to 50% by weight, based on the esters of thiocarboxylic acids - Is, the range of 20 to 30 wt .-% is particularly preferred is.

The textile smoothing agents according to the invention, with and without additional antioxidants d), due to their high thermal stability, among other things can be used in spin finishes. Another subject of The present invention is therefore spin finishes for synthetic filaments, characterized in that they have the described thermostable contain textile smoothing agents. The textile smoothing agent in turn may contain the additional antioxidants d). 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 those known from the prior art Auxiliaries such as thread closing agents, pH regulators, bactericides and / or anti-corrosion agents.

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.

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.

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.

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 of textile smoothing agents according to the invention,

b) 0 to 65% by weight of 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.

example A) Production of the textile smoothing agent according to the invention AA) pentaerythritol tetrapelargonate with 5% by weight pentaerythritol tetrakisoctylthiopropionate

In a 3 liter three-necked flask equipped with a stirrer, water separator and Nitrogen bubbling became 1670 g (10.44 mol) of pelargonic acid, 344 g (2.53 Mol) pentaerythritol, 1 g 50% by weight hypophosphorous acid and 101 g pentaerythritol tetrakisoctylthiopropionate given and stirred at 200 ° C. After this the esterification was practically complete, the remaining acid was removed, the product cooled and treated with 40 g calcium silicate. After Filtration gave liquid product.

AB) pentaerythritol tetrapelargonate with 4% by weight pentaerythritol tetrakisoctylthiopropionate and 1% by weight Irganox ^R 1010

Analogously to AA), 1699 g of pelargonic acid, 350 g of pentaerythritol, 1 g of 5% by weight hypophosphorous acid, 82 g of pentaerythritol tetrakisoctyl propionate and 20.5 g of Irganox ^R 1010 were reacted and worked up.

AC) Pentaerythritol tetrapelargonate with 2% by weight diisotridecylthiodipropionate and 1% by weight Irganox ^R 1010

Analogously to AA), 1719 g of pelargonic acid, 355 g of pentaerythritol, 1 g of 50% by weight hypophosphorous acid, 41.5 g of diisotridecyl thiodipropionate and 20.7 g of Irganox ^R 1010 were reacted and worked up.

B) Investigation of thermal stability BA)

The thermal stability was determined by means of a bowl test. For this purpose, 3 g of substance were placed in an aluminum dish and exposed to a temperature of 250 ° C. in an oven for 3 hours. Then it was determined how much of the substance (in%) is still present after the thermal treatment. The higher the value, the better. The pure pentaerythritol full ester of pelargonic acid without any addition of antioxidants served as a comparison (comparison). example % Residue comparison 69.8 AA) 76.7 FROM) 96.6 AC) 89.2

BB)

Long-term thermal stability was determined using the Thermogravic Analyzes method (TGA isothermal method); with thermo balance TGA 951, DuPont, at 230 ° C after 10, 13 and 16 hours. Here too, the residue of the substance was given in% after the thermal treatment. The higher the value, the better the result. example % Behind 10th 13 16 hours comparison 48.1 42.3 38.7 AA) 52.1 48.6 46.0 FROM) 83.4 78.6 74.0 AC) 66.0 52.1 43.2.

The application examples show that the textile smoothing agents according to the invention have a higher thermal stability than the pure ester (comparison), despite only minor additions to the thiocarboxylic acid esters. Furthermore shows that the addition of the smallest amounts of the sterically hindered Phenols synergistically improve thermal stability (see AB) and AC)). In addition, when using the invention textile smoothing agent the residues lighter colored and more liquid than comparable ones Esters without the addition of the esters of thiocarboxylic acids.

Claims (11)

1. Thermally stable textile lubricants obtainable by reaction of

   a) polyols with

   b) fatty acids containing 6 to 22 carbon atoms

   in the presence of 0.05 to 8% by weight, based on the sum of components a) and b), of

   c) esters of thiocarboxylic acids corresponding to general formula (I) and/or (II): R¹ - S - R² - COOH HOOC - R³ - S - R⁴ - COOH

   in which R¹, 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.
2. Lubricants as claimed in claim 1, characterized in that the polyols 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 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 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 aliphatic monohydric C_1-22 alcohols, 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 a C_6-18 alkyl group and R² is a C₁ or C₂ alkyl group.
7. Lubricants as claimed in any of claims 1 to 6, characterized in that, in formula (II), R³ and R⁴ represent a C₂ alkyl group.
8. Lubricants as claimed in any of claims 1 to 7, characterized in that the thiocarboxylic acid esters are present in a quantity of 0.5 to 5% by weight and, more particulary, 1 to 3% by weight, based on the sum of components a) and b).
9. Lubricants as claimed in any of claims 1 to 8, characterized in that antioxidants, preferably sterically hindered phenols, are additionally present as an additive d).
10. Lubricants as claimed in any of claims 1 to 9, characterized in that the antioxidants are present in a quantity ratio to the thiocarboxylic acid esters of 1:1 to 1:4.
11. Spinning finishes for synthetic filaments, characterized in that they contain the thermally stable textile lubricants claimed in claim 1.