DD296974A5 - WEAR ANIMATED ANTISTATIC - Google Patents

Abstract

The invention relates to a anti-wear antistatic agent, which is used for the production of temperature-resistant, antielstatically effective and strong anti-wear Syntheseseidenpraeparationen. The aim of the invention is to further increase the antistatic, antiwear-reducing effectiveness of the preparation. The object of the invention is to improve the use value of Syntheseseidenpraeparationen. According to the invention, the anti-wear agent is characterized by a product mixture of sulfobetaine sulfonate and sulfobetaine which is formed from allyl ammonium salts of oxyethylated fatty amines of the chain length range C12 to C20 by sulfosulfination and subsequent complete or partial oxidation. The application of the invention takes place in the synthesis silk manufacturer. Formulas VI to VIII {antistat; Verschleiszinhibitor; temperature resistance; Heizschienenvercrackungsinhibitor; sulfobetaine; Sulfobetainsulfinat; Sulfobetainsulfonat; Polyester silk}

Description

(CH CH_0) H

CH - CH - CH_ -

(VIII)

(CH CH O) H

2 2 ш

50

as 20 to 30% aqueous or glycolic solution in an amount of 0.8 to 5.0%, based on the preparation concentrate, is used.

Field of application of the invention

The invention relates to a wear-reducing antistatic agent, which is used for the production of temperature-resistant, anti-electrostatic effective and highly wear-reducing Syntheseseidenpräparationen.

Characteristic of the known state of the art

After glue, antistatic agent for fiber preparation, in: man-made fibers / textile industry, 36./88. Vintage, Issue 9/86, pp 684-688, salt-like, polar substances are mostly used as antistatic agents; For example, phosphoric acid mono / di-ester salts, phosphonic acid ester or -haibester, alkansulfonsaure salts, alkyl sulfates, petroleum sulfates, sarcosides, betaines, sulfobetaines, amine oxides, quats of all kinds. All these products have advantages in addition to numerous disadvantages, eg. For example, it has been proven that with certain formulations a formulation-dependent wear effect on the thread guiding and guiding organs occurs (Peschel, lecture at the VII. CSSR Conference "Avivagen, preparation and sizing emitter, 8.11.1981, Pardubice). The quaternary ammonium salts of the formula I proposed in the patent specification, for example DE 3138181, DE 3321608, EP 90117,

CH-CH-O) H 2 2 b

- (CH _- -CH _- -O) - CO - RA

(CH-CH -O) H

ώ 2 с

in which R _{t is} alkyl radicals having 12 to 23 carbon atoms, R _{2 is} alkyl radicals having 8 to 21 carbon atoms and A "is an Anton of an organic carboxylic acid (b, с = 1 to 3), have due to their salt structure according to own investigations not sufficient temperature resistance for the preparation of polyamide and polyester silks from Kordtyp after the spun draw winch process at temperatures over 200 ⁰ C. in parallel, their wear-reducing effect for matt synthesis Seiden above 200 ° C does not sufficiently

 Also amine oxides according to formula II,

(ID

in which R ₁ and R _{2 are} polyethylene oxide units and R _{3 is} alkyl of 10 to 18 carbon atoms, have for high-temperature processes not sufficient antistatic and wear-reducing effect. In contrast, phosphoric acid mono / di-ester salts (formula HIa or HIb, wherein RA ^ yI (C ₁₀ -C ₁₈ MO-CH ₂ -CH ₂ ) Ii-O) and Phosphorsäurehalbestersaize of oxyethylated fatty alcohols with sufficient antistatic effect on Syntheseseiden to disturbing signs of wear on the thread guide organs and to disruptive degradation reactions with reduction of the antistatic effect in high-temperature processes.

(НІЬ)

; -: - О - F One (IIIaj F-O-P- OMe

OMe OB

These interfering side reactions cause pure Phosphorsäuretriester according to formula IV,

(RO) ₃ P = O (IV)

where R has the same meaning, and not phosphoric diester. However, they also do not have sufficient temperature-resistant antistatic activity even in high-temperature processes.

As a result of thermohydrolytic degradation, the fatty alcohol sulfates or alkanesulfonates which are also frequently used tend to form inorganic salts. Contrary to the statement by Kleber in the article Antistatika for fiber preparation, in: man-made fibers / textile industry, 36./88. Vintage, Issue 9/86, page 684-688, lead the resulting acid salts, but no neutral salts such as sodium sulfate, to the wear of thread guide organs, Galeiten or heaters.

It has already been proposed by us for the production and further processing of matted and unmattid synthetic high polymer filaments, e.g. B. based on polyamide or polyester silk, on textile machines of different technologies to use preparations, the 3-Sulfopropylammoniumbetaine the general formula V.

R - Ν - CH ^ - CK ^ - CH

(V)

as anti-electrostatic wear inhibitors, wherein Ri is a long-chain alkyl radical and R ₂ and R _{3 are} polyoxyalkylene radicals. Oxethylated 3-Sulfopropylammoniumbetaine of formula V are prepared according to DD-PS 154443. These substances must be homogenized before use as preparation components only at temperatures between 40 and 50 ⁰ C with stirring. Another disadvantage of the preparation components characterized by formula V is that their solubility in oily systems for the preparation of preparation concentrates is too low. By using the specified in JP-PS 56-86148 2-Hydroxysulfopropylammoniumbetaine or the fluorine-containing alkylsulfobetaines according to DE-PS 3104766 and alkyl sulfobetaines according to DE-PS 3138770 occurs no improvement.

Object of the invention

The object of the invention is to overcome the disadvantages of the previously proposed compounds as antistatic agents and replace them with components that have C very good antistatic and wear-reducing properties at both room temperature and at temperatures above 200 ^0th Based on local raw materials, eg. B. Tierkörperfettamingemischen preparation components of sufficient solubility, homogeneity, storage stability can be developed with incorporation into preparation concentrates, which leads to an improved utility of the Syntheseseidenpräparation with the same or reduced raw material costs. It should be achieved a very good anti-electrostatic effectiveness in all process stages and, associated therewith, minimal wear of the thread guide members. The pour point of the preparation prepared with the antiperspirant antistatic agent according to the invention should be lowered to below -5 ° C in order to allow the low thread temperatures occurring in the polyester high speed spinning wind process with thread-locking effect (GUBEN method) without disadvantage.

Explanation of the essence of the invention

In order to achieve the above objective of the invention, the object was to obtain more suitable wear-reducing preparation antistatics on domestic raw material base, preferably of animal body fatty amines for synthetic fibers, which offer the economic and technical advantages mentioned in the objective and, above all, by the improved properties and effects of the already differentiation of proposed preparation components. In the foreground of the task was the ease of incorporation into preparation concentrates and the increase of the use value of the preparations as well as very good antistatic effect combined with minimization of wear regardless of the processing temperatures used.

According to the invention the object is achieved in that from allylammonium oxyethylated fatty amines of the chain length range C ₁₂ to C ₂₀ , preferably C ₁₆ to C ₁₈ , by sulfosulfination with hydrogen sulfite / oxygen available product mixtures of 20 to 60mol .-% Sulfobetainsulfinat and 40 to 80Mol .-% Sulfobetaine be oxidized with a Sulfobetainsulfinatanteil molar corresponding amount of oxidizing agent.

The antiperspirant antistatic agent obtained in this case is composed of 20 to 60 mol% of sulfobetaine sulfonate of the general formula VI

ί. CH ₀ CH ₂ O) H

(Vl)

.. CH _л - CH - СК _о - SO

¹ I. ι _ * *

(СН ^ СН ^ О.) H SO ^

and from 40 to 80 mol% of sulfobetaine of the general formula VII

.- f "< t; i" 4T_j / '. -, rj

R ₁ - n "CH ^ - сн ^ - си. - so_ (νιο

(CH CH 0) H Z И га

together in which R _{1 is} alkyl radicals having 12 to 20 carbon atoms, preferably alkyl radicals of predominantly in animal body fat amines chain length range C ₁₆ to C ₁₈ and η + m integers from 2 to 10, preferably 3, mean. The antiperspirant antistatic agent is used in the form of a 20 to 30% solution in water or ethylene glycol to the preparation concentrates in an amount of 0.8 to 5% Tensidaktivsubstanz, calculated on the preparation concentrate. The preferred ratio of the mixture components of the antistatic agent corresponding to the components according to formulas VI and VII is 1: 1. For special Einsaugebiete is also an antistatic mixture of substances of the formula Vl and VII and formula VIII (in formula VIII R ₁ and η + m have the meanings given for the formulas Vl and VII)

(CH GH 0) H

--N CH ₉ - CH - CH ₉ - S0 _q , ν ,,,.

(CH ... CH 2 O) H SO.

in the ratio of 5: 2.5: 2.5 has been used successfully.

Such mixtures are obtained, as described above, when a portion of the original sulfobetaine sulfinate component (VIII) is retained by the use of a deficient oxidizing agent.

As an additional surprising advantage of the inventive solution has been found that the above sulfobetaine sulfonate / sulfobetaine mixture may additionally contain up to 40% of inorganic and / or organic neutral salts without adversely affecting the antistatic and wear-reducing effect of the invention. This opens up possibilities of additional increase of the anti-electrostatic effect and the possibility of adding biocides and

Heizschienenreinigungsverstärkern.

The achievement of the object of the invention, the objective is achieved in all respects.

embodiments

Synthesis of Antiperspirant Antistatic Sulfobetainesulfonate / Sulfobetaine 1: 1 Component Mixture of Hexadecyl / octadecyl-bis-fpolyoxyethylent ^^ - disulfopropylammonium betaine and hexadecyl / octadecyl-bis (polyoxyethylene) -3-sulfopropyl-ammonium betaine R ₁ = C ₁₆ H ₃₃ / C ₁₈ H ₃₇ ; η + m = 3 in the general formulas VI and VII

CH CH CH 0) HI 2 Ί η

R - vC CH - CH - CH - SO

(CH CH 0) H 2 2 in

ίCK CH O) H 'j ν 2' η

CH - CH - CH ,, - S0 "2 ν _ώ о

(VII)

(CH CH O) H

2 2 m

In a commercially available 5 m ³ stirred tank, fused oxethylated carcass fatty acid Präwozell 1618/3 (trade name of VEB Chemische Werke Buna for a primary fatty amine ethoxylated with 3 moles of ethylene oxide) water, allyl chloride (85 mole% per mole of preweened 1618/3; this Allylchlorideinsatzmenge corresponds to the alkylatable nitrogen portion in the technical ethoxylated amine) and catalytic amounts of sodium bromide (alkylation catalyst) mixed together and reacted by heating (50 to 85 ⁰ C) to 25 to 35% solution of ethoxylated allylammonium salt.

By addition of 40% sodium bisulfite technical solution (1.9 moles of NaHSO ₃ per mole of allylammonium salt) and introducing a moderate compressed air flow and maintaining a solution pH by 4, the allylammonium salt starting at 30 ° C in the course of 24 hours to Sulfobetainsulfinat / Sulfobetaine mixture partially sulfosulfiniert. It is then neutralized with sodium hydroxide solution and the sulfinate is oxidized by the addition of half molar amount of sodium hypochlorite (calculated on used Präwozell 1618/3) to Sulfobetainsulfonat. After completion of the oxidation, the pH is adjusted to 7.5 to 8.5. Upon cooling to 20 ° C, the antiperspirant antistatic solidifies like a gel.

example 1

Schäröl for deeply matted polyester silk

The preparation according to the invention consists of:

41.2% alkylpolyol ethers with 8 ethylene oxide units, wherein the alkyl radical is characterized by the chain length range from Cie to Cte;

12.3% iso-nonylphenol-alkylene glycol ethers having 10 propylene oxide units and 10 ethyleneoxy units in the molecule; 16.5% iso / n-butyl stearate mixture;

15.0% sulfobetaine sulfonosulfosulphite mixture

of the formulas VI and VII in the ratio of the components of 1: 1, wherein R _{1 is} an alkyl radical having 16 to 18 carbon atoms and η + m = 3 (20% aqueous solution);

15.0% diethylene glycol.

With a run of 1% warlock oil on the Mayer warping machine, the following values listed in Table 1 were achieved for the titer used PE-SSW-tm 5 tex f 20 *, which were compared to known phosphoric ester antistatic agents with the same active substance content.

The wear values were determined on the running yarn in the laboratory according to DD-PS 155356, while the electrostatic charge was measured directly on the running warper.

Table 1

Preparation wear note, anti-electrostatic

determined after charging, measured

DD-PS 155356 with static voltmeter

the company Rothschild

commercially available warping oil 3 80-100 V

for Mayer-stretching warping machines

commercially available phosphorus 4 40-60 V

acid triester with mono- / Diesteranteilen as preparation component

1 OV according to the invention

preparation

* (Polyester fast spinning windbreaker for deep-matte polyester silk)

Example 2

Polyester Rapid Spin Preparation for Stretch Texturing (Polyester Rapid Spin Winding / Stretch Texturing) To improve the running properties of preparations with the z.Z. used commercial product consisting of 80% Alkylalkylenoxidaddukten, 15% amine oxide and 5% technical Phosphorsäuretriester (Preparation A), were for antistatic properties, wear minimization and tendency to crack modifiers B, C, D at the titer PE-SSW normal matt 16.7 tex f 32 tested. The application of the preparations A to D was carried out as a 15% aqueous solution.

Table 2 modifier wear Antielektrosta Vercrackungs- Präpa (Amount and type) note, be table charging gradderPri- ration agrees after the primary märheizer DD-PS 155356 heaters at 200 ° C (visually be with static volt Right) meter of the Fa. Rothschild without 3 180-200V brown, A greasy after 3 weeks 2.5% oleyl 2 70-90V black ver B sarcoside; crusting after 97.5% A 2 weeks 2.5% phosphorus 4 50-70V brown to C phorsäure- black ver mono-Zdiester- crusting after salt; 3 weeks 97.5% A 2.5% experience 1 10-30V minimal bright D dung contemporary scab formation antistatic agent; after 6 weeks 97.5% A

Only by the mixture "D" according to the invention were very good processing properties in the stretch texturing achieved (minimal cracking of the heating rails, low cleaning effort)

Claims (3)

1. Wear-reducing antistatic agent for synthetic silk preparations, characterized in that it is a mixture consisting of 20 to 60 Mol.- ⁰ / "a compound of the general formula VI i CH Oj H CH CH (.CH ₀ CH ^ O) H SO. ί-- £ - Ш О and 40 to 80 mol% of a compound of the general formula VII (CH CH 0) H 2 2 η fCH Cn O) H '2 2 ' m where R _{1 is} an alkyl radical having 12 to 20 carbon atoms and η + m is an integer from 2 to. 2. Anti-wear antistatic agent according to claim 1, characterized in that the quantitative ratio of the compounds according to formula VI and VII is equal to 1. 3, Method for applying the anti-wear antistatic agent according to claim 1 and 2, characterized in that the mixture of compounds of formula Vl, VII and VIII (On Oil U } H R - N CH - CH - CH - SO i.CH_CH 0) H SO. (CH CH 0) H, 2 2 η CH - CK - CH - SO 2 2 2 (VII) (CH_CH_O) H