DE2744021C3 - Concentrated aqueous agent for rendering synthetic fiber materials antistatic and its use - Google Patents

Description

A) a water-soluble reaction product that by Implementation of 1 mole of the bischlorohydrin ether of ethylene and / or diethylene glycol (I) with 0.2 up to 1 mol of a compound of the general formula (II)

A major disadvantage of synthetic fibers is known to be their electrostatic chargeability. It There has been no lack of attempts to remedy this negative property by treating it with the most diverse to eliminate ionic and non-ionic compounds. The well-known products that are z. B. to alkanolamines or their salts (see z. B. US-PS 29 85 543), ethoxylation products of in particular amines or their salts (stand z. B. Chemical Abstracts Volume 77, 1972, page 50.092, No. 50089 w) or reaction products of reactive amino groups and containing polyalkylene oxide radicals Polyamines with compounds that contain more than one epoxy and / or halohydrin group in the molecule (See US-PS 3108 011), but have the decisive disadvantage that the rubbing fastness of the usually with disperse or pigment dyes dyed synthetic fibers is significantly deteriorated.

H ₃ _ "N- (C _v H _2t OH)"

in which x = 2 or 3 and n = 1, 2 or 3, in The presence of 0.8 to 1.7 moles of alkali hydroxide and at least 13 moles of water has been produced, possibly in combination with B) a compound of the formula (III)

R -

in which R is a branched or straight-chain hydrocarbon radical with 1 to 5 carbon atoms, which can also be substituted by OH groups can, or the rest

-R'-COO-X +

¹ 'where R ^{1 is} a saturated or unsaturated hydrocarbon radical with 2 to 4 carbon atoms, which can also be substituted by OH groups, and X ^{4 is} an equivalent of a cation,

Vi contains.

In addition, the agent is used for rendering synthetic fiber materials antistatic, this being used in a dilute aqueous solution is placed under protection.

> i The bischlorohydrin ethers of ethylene and / or diethylene glycol used to produce the antistatic agent are prepared in a known manner by reacting 1 mole of the glycol with 2 or more than 2 moles Epichlorohydrin produced. In particular are

Surprisingly, those bischlorohydrin ethers are suitable in which epichlorohydrin is in excess to the glycol, particularly preferably ethylene glycol, in Presence of strong acids, such as sulfuric acid, hydrochloric acid or perchloric acid, as catalysts

h) device. This accumulation is generally at The reflux temperature is carried out for 3 to 6 hours. The excess epichlorohydrin will finally removed. The epoxy number of the obtained

Bischlorhydrinäthers should not exceed a value of 0.08. The term bischlorohydrin ether includes also technical compounds in which less than 2 moles of chlorohydrin residues per mole of ether are present.

The alkanolamines used have the formula ί (II). Compounds of the formula (II) which are preferably used are those in which n = 3 , that is to say the tertiary alkanolamines, the triethanolamine having proven particularly suitable. These compounds, like the starting compounds, are used to produce the substances (I) in technical quality.

Ethylene glycol bischlorohydrin ether is preferably used as compound (I) and triethanolamine as compound (II), since the! Condensations- ι ϊ product when used as an antistatic agent has a very good antistatic effect and practically none Bringing deterioration in the rub fastness of the dyed synthetic fibers.

The compound «« »(I) and (II) are in the molar ratio-> o nis; 1: 0.2 to 1, in particular I: 0.25 to 0.45 implemented

The reaction is carried out as follows: the bischlorohydrin ether (I) is initially introduced, diluted with water and the compound (II) is added at normal to slightly elevated temperature. Then 2> 0.8 to 1.7 mol per mol of compound (I) of alkali metal hydroxide (sodium and potassium hydroxide are mentioned in particular), preferably in the form of a concentrated aqueous solution, and several hours at an elevated, usually reflux temperature (between - in see 100 and 125 ° C / condensed. The amount of water used for dilution and the amount of water introduced by the concentrated alkali hydroxide solution is at least 13 mol, • ■ • a special 25 to 70 mol per mol of compound (1). This amount of water η is necessary to avoid polycondensation.Finally, it is cooled and, if necessary, adjusted to a pH of about 73 to 9.0 with further alkali or acid, e.g. acetic acid to filter the end product before use. The concentrated aqueous agents obtained in this way have a dry matter content of about 15 to 55% by weight.

The erfindurtgsgemäßen agents for the antistatic finishing of synthetic fibers in wässeri- 4 "ger solution used sub-synthetic fiber materials are both all shaped articles, in particular woven or knitted fabric made of pure synthetic materials, such as polyacrylonitrile, polyester, or polyamides, as well as acetate, ie v> Cellulose di-bis-triacetate. as well as mixtures of these materials with natural or regenerated cellulose fibers, wool or other natural fibers, the proportion of synthetic fibers being the same or predominant in the mixed articles. These materials are normally colored with pigment · and dispersion paint * Steffen before the final finishing and packaging

For the antistatic treatment of synthetic Fibers, the M) agent prepared as described above is diluted with water. The amount used largely depends on the material to be finished and the chosen application method. in the In general, the liquor should contain so much of the agent that the dry layer after finishing of antistatic component is 0.1 to 2% by weight, based on fiber. The material is made according to known methods such as soaking and Treated by squeezing, spraying or splashing, etc., dried and usually condensed at 120 to 160 "C for a few minutes.

Optimal antistatic effects and a particularly favorable rubbing fastness behavior are achieved when the Agents prepared as described above with compounds of the formula (III)

R-C00-X ^H

(III)

in which R is a branched or straight-chain hydrocarbon radical with 1 to 5 carbon atoms, which also may be substituted by OH groups, or preferably the remainder

-R'-COO-X +

where R ^{1 is} a saturated or unsaturated hydrocarbon radical having 2 to 4 carbon atoms, which can also be substituted by OH groups, and X ^{+ is} an equivalent of a cation, are used in combination. X ⁺ is preferably an equivalent of an alkaline cation, while R is in particular the remainder

-CH = CH-COOX +

means Sodium acetate, ammonium propionate and sodium butyrate are used as compounds of the formula (III) and sodium capronate, but preferably alkali salts of saturated or unsaturated dicarboxylic acids with a total of 4 to 6 carbon atoms, such as disodium adipate, dipotassium tartrate and, in particular, disodium maleate The compound (III) is used in the finishing liquors in amounts of 4 to 30 percent by weight, based on the dry substance of the antistatic. added

It is of course also possible to incorporate the compound (III) into the agent right from the start incorporated a In this case, the salts or the Starting substances of the same are added during cooling and only then is the final pH set.

The object of the present invention offers the advantage that when equipping the usually Synthetic fibers dyed with disperse and pigment dyes have very good antistatic properties Equipment with a pleasant grip at the same time is obtained, the rubbing fastness almost completely is retained According to the state of the art, the resistance to rubbing of the antistatic finish falls by several Grades. This is associated with the disadvantage in practice that when the textiles are used, a The dye is rubbed off and, as a result, other textile goods, such as underwear and upholstery fabrics, become unsightly.

In the following examples, the rubbing fastness is according to DIN 54 021 (assessment according to grades 1-5) and the antistatic effect was determined with the »Rothschild static voltmeter«. The voltages give the static charge generated by rubbing an iron rod five times. The half-life is the To understand the time in seconds within which the original voltage has dropped by half.

Example I. a) Production of the bischlorohydrin ether

While cooling, 65 g of concentrated sulfuric acid in 756 g of ethylene glycol are first added in a thin stream stirred in. This mixture is then stirred into 5300 g of epichlorohydrin at room temperature.

after the whole ca 5 hours under reflux (about 120 ⁰ C) is treated and then cooled to 25-3O ⁰ C. Thereafter, about 3500 g of epichlorohydrin are removed by distillation under vacuum, namely at up to 6O ⁰ C and about 10 x 1.33 m bar pressure. Finally, it is cooled to room temperature.

The produced bischlorohydrin ether has a Epoxy number of 0.035 uuf.

b) Production of the antistatic agent

1) 233 g of the Bischlorhydrinäthers prepared under a) are initially introduced together with 625 g of water, heated to 35 to 40 ⁰ C and 36 g of triethanolamine were added. Then 75 g of 50% aqueous sodium hydroxide solution are allowed to flow in over the course of about 20 minutes. The whole is then kept at reflux temperature for 3 hours and then cooled (pH = 8.2).

2) Half of the agent prepared under b) is heated to 75 to 80 ⁰ C in portions, 6.5 g of maleic anhydride was added and then immediately added to 10 g of 5O ° / o aqueous sodium hydroxide solution with stirring. After about 20 minutes, the ^{mixture is cooled to 30 °} C. and filtered. The pH of the end product is approx. 8.0. J-.

c) Antistatic equipment

A colored in the usual manner with a commercially available disperse dye-polyester knitted fabric is padded with given below fleets "ι (liquor pick-up 50%), at 100 ⁰ C dried and condensed for 5 minutes at 140 ⁰ C.

The composition of the fleets is as follows:

A) 55 g / l medium b 1)

B) 50 g / l medium b 2) '"'

C) 32 g / l of the according to Example II A) of US-PS 31 08 011 produced antistatic (approximately the same dry substance content as in liquors A and B).

D) 76 g / l of the according to Example 1 of CH-AS 17 616/71 produced product, but with polyethylene glycol 400 for the production of the polyglycidyl ether is used and no emulsifier is added (approximately the same dry matter content as in Fleets A and B).

The test of the antistatic effect and the rubbing fastness shows the following result:

fleet invention
according to Rcib-
cchlhcit Static
Fully Charging
llalbwcrt / cit Al
Bl State of
technology 14th
14-5 0
0 0
0 C. State of
technology 2 0 0 D. unbchandcit 3 0 0 5 IO > 3ÖÖ

Example 2
a) Production of the antistatic agent

I.) As indicated in Example 1 under b 1), an agent is made using the same amount of bischlorohydrin ether, 900 g of water, 108 g of triethanolamine and 100 g of 50% strength aqueous sodium hydroxide solution were prepared (pH = 8.8).

2.) As described in Example I under b 2), a Means made with the addition of 20 g of maleic anhydride and a correspondingly increased amount of sodium hydroxide solution

b) Antistatic equipment

A polyamide taffeta (80 g / m ² ), which is dyed in the usual way with an orange pigment (color index 21 115), is mixed with liquors containing 55 g / l of agent a I) (liquor A) or 50 g / l of des means a 2) (liquor B) containing, impregnated, squeezed to 50% wet pickup, dried and kondeusiert 3 minutes at 130 ⁰ C. The test results (antistatic effect and rubbing fastness) are shown in the following table:

Fleet Rcibcchthcit Static charge Volt I lalbwcrtzcil

0
130

A. 4-5 2 B. 5 0 untreated 5 14th

As can be seen from the table, the inventive! Equipment with the fleets A and B one compared to the state of the art (fleet C and D) Considerable improvement in terms of judgment.

Example 3
a) Manufacture of bischlorohydrin ether

In the manner indicated in Example 1 a) is a Bischlorohydrin ether from 10MoI diethyl glycol and 50 moles of epichlorohydrin produced.

b) Production of the antistatic agent

270 g (about 1 mol) of the bischlorohydrin ether prepared under a) are poured into 60 mol of water and heated to approx. 45 ° C. Then 0.4 moles of triisopropanolamine are added added and allowed to flow in 120 g of 50% sodium hydroxide solution over a period of about 30 minutes. the The mixture is then refluxed for 4 hours, then cooled and filtered.

c) Antistatic equipment

A cotton polyester mixed fabric 33:67 (150 g / m ² , dispersion-dyed with the dye Colorindex Dispersblue 54) is soaked and squeezed off with an aqueous liquor containing 100 g of the agent prepared under b) and 6 g of sodium tartrate per liter (liquor uptake 75%) , dried and condensed at 130.degree. C. for 5 minutes, "The fabric exhibits a permanent antistatic finish, a soft handle and, in particular, practically no reduction in the thickness compared to the non-woven fabric.

Example 4
a) Production of the antistatic agent

In the manner described in Example IbI) is a Means prepared, but otherwise the same conditions 0.5 mol Mvjnoätlianoliimin (al) b / .w. 0.5 mole Diethanolamine (a 2) can be used instead of triethanolamine.

7 8

Instead of the mono b / w [) iiilliannl; unins k.iiin in (Ικ · 2 "> g <1 des iiiiIlt a) herpesd'Hlon MiMcIs (; ι I) and

in the same way J-Aininoprnnamil (I) b / \\. Diisnpmpa / iisiil / liih I μ. I kiiliiimpKkiiliit cnlliiill. fouliirilici I

nokiniin / nr llcrstclluny des Millcls Ικ · ι \ ιη>; ινομι · η (I lollciiiiiilnMlinic bV '/ n), at 140 C in a / ιιμ

will. fellnifknei iiiul erliil / l. l); is behiiiulellu (lewcbc «cisl

... ,, .. · cmc good iinlisliilisclic AiisriisliiiiL'iiuf.

b) Anlisiiiiisclie AiisnisiiuiL '. ■. ...,., ..

In ί-'lciilici manner kiinn cmc I loiie inner l.msiit / des

Lm mn a usual l) is |) crsionsfiirbslofl ^ 'cl.iibics means (; i 2) bcrciicl, where iiiiih the Aiisni ·

lOKiicrvlnitrilgewehc and with a white moth. stung also result in pill l-lffekle.

Claims (2)

Patent claims: 1. Concentrated, aqueous agent for rendering synthetic fiber materials antistatic, characterized in that it acts as an antistatic component A) a water-soluble reaction product that is produced by the reaction of 1 Mo! of the bischlorohydrin ether of ethylene and / or diethylene glycol (I) with 0.2 to 1 mol of a compound of general formula (II) H ₃ ^ ₁ N- (C ₁ H _2x OH) ,, in which x = 2 or 3 and n = 1, 2 or 3, in the presence of 0.8 to 1.7 mol of alkali metal hydroxide and at least 13 mol of water has been prepared, optionally in combination with B) a compound of the formula (HI ) R-COQ-X ⁺ (III) in which R is a branched or straight-chain hydrocarbon radical with 1 to 5 carbon atoms, which can also be substituted by OH groups, or the radical -R'-COO-X + wherein R ^{1 is} a saturated or unsaturated hydrocarbon radical with 2 to 4 carbon atoms, which can also be substituted by OH groups, and X ^{+ is} an equivalent of a cation, contains. 2. Use of the agent according to claim 1 for Antistatic rendering of synthetic fiber materials in a dilute aqueous solution is used. 3- Use according to claim 2, wherein an agent is used which does not contain the compound B) and the compound B) is added separately to the dilute aqueous treatment solution. A similar procedure is found in CH-AS 17 616/71 known for rendering synthetic textile fibers antistatic, in the case of preparations that are water-soluble or water-dispersible polycondensation pro- '. products made from polyglycidyl ethers of polyols and water-soluble amines and an organic solvent included. Wash-resistant antistatic effects are achieved. The known But the method also has the disadvantage that the the rubbing fastness of the dyed synthetic fiber materials is adversely affected by the finish. We have now found a means of rendering synthetic fiber materials antistatic which does this Does not have any disadvantage. ι «is the subject of the present patent application a concentrated, aqueous, antistatic agent for synthetic fiber materials which is characterized as being antistatic acting component