DE1619084C3 - Washing and dry cleaning resistant, antistatic finishing of textile material - Google Patents

Description

for washing and dry cleaning resistant, antistatic finishing of textile material in accordance with Main patent 1619 082, characterized in that condensation products can be used in which the lipophilic radicals are wholly or partially formed by polysiloxane radicals will.

2. Use of condensation products according to claim 1, characterized in that Condensation products are used in which at least 10, preferably at least 50, and up to 100 mole percent of the lipophilic residues are formed by polysiloxane residues.

3. Use of condensation products according to claims 1 and 2, characterized in that that condensation products are used in which the total amount of lipophilic Hydrocarbon residues and polysiloxane residues 2 to 65, preferably 6 to 30 percent by weight, of the condensation product.

4. Use of condensation products according to Claims 1 and 3, characterized in that that in the condensation products used, the lipophilic polysiloxane residues 5 to Contain 10 or more silicon atoms.

5. Use of condensation products according to claims 1 to 4, characterized in that that in the condensation products used those present in the starting components 50 to 80% of reactive amino or halohydrin groups have reacted.

6. Use of condensation products according to claims 1 to 5 for antistatic Finishing of synthetic fiber materials in an aqueous liquor with the use of Acid acceptors.

The invention relates to the use of water-soluble or water-dispersible curable Condensation products, the hydrogen atoms bonded to amino nitrogen atoms and halohydrin ether groups as well as lipophilic residues for washing and dry cleaning resistant antistatic Finishing of textile material, especially those made of synthetic fiber materials or with a proportion of synthetic fiber materials.

The subject of the main patent 1619 082 is the use of water-soluble or in water dispersible, curable condensation products, ίο the hydrogen atoms bound to amino nitrogen atoms and halohydrin ether groups in a ratio of 1: 0.6 to 1: 1.5 and lipophilic radicals with at least Contains 8 carbon atoms and which are produced by the condensation of

a) ammonia and / or primary monoamines and / or at least two amino hydrogen atoms containing polyamines and

b) Di- and / or polyhalohydrin ethers of di- and polyalcohols with 2 to 6 carbon

atoms and / or the addition products of 1 to 2 moles of alkylene oxide, preferably ethylene oxide, with these alcohols,
wherein at least one of the reacting components is wholly or partly due to the lipophilic

Is substituted and wherein the amino or halohydrin ether groups of the starting compounds have reacted to 20 to 90%, preferably 50 to 70%,

for washing and dry cleaning resistant, antistatic finishing of textile material.

The invention has a further embodiment of the subject matter of the main patent, but in particular an improvement in wash resistance and handle, as well as a further reduction in the tendency to graying in dry cleaning fleets.

The solution to this problem consists in an amendment the use of water-soluble or water-dispersible curable condensation products bound to amino nitrogen atoms Hydrogen atoms and halohydrin ether groups in a ratio of 1: 0.6 to 1: 1.5 and lipophilic radicals with at least 8 carbon atoms, for washing and dry cleaning resistant antistatic Finishing of textile material according to patent 16 19 082, which is characterized by that condensation products are used in which the lipophilic radicals wholly or partially of Polysiloxane residues are formed.

The condensation products of the main patent are produced by conversion (condensation) from

a) ammonia and / or primary monoamines and / or at least two amino hydrogen atoms containing polyamines and

b) Di- and / or polyhalohydrin ethers of di- and polyalcohols having 2 to 6 carbon atoms and / or the addition products of 1 to 2 moles of alkylene oxide, preferably ethylene oxide, of these alcohols,

wherein at least one of the reacting components is wholly or partly due to the lipophilic Radicals with at least 8 carbon atoms is substituted,

at elevated temperatures, optionally in the presence of water, organic solvents and

3 4

acid-binding agents, the amino or solution in the usual manner in the pad, dipping or Halohydrin ether groups of the starting compound spray process used, with about 0.3 to fertilize to 20 to 90%, preferably 50 to 70%, 5 percent by weight of the condensation product - over-react, drew on the fiber weight - on the textile material

The polysiloxane residues 5 used according to the invention are applied.

containing condensation products are in ana- Particularly advantageous the products in

Logically produced by converting Ammo as a result of its good affinity for textile fibers from long

Apply niac and / or amino compounds with halogen liquor in the exhaust process. they pull

hydrin ether compounds, but with the under- already at relatively low temperatures

it was decided that reaction components are used, 10 (20 to 100 ⁰ C, preferably 40 to 70 ⁰ C) even without

instead of lipophilic hydrocarbon residues, the addition of drawing aids to the textile fibers.

Contain polysiloxane residues. There are at least 10, the liquor ratio can be 1: 8 to 1: 100,

preferably 50 to 100 mole percent of the lipophilic.

Compounds containing hydrocarbon radicals are regulated by ionic or non-ionic wetting agents

of the main patent through the polysiloxane residues. Both the block or. Dip spin process

holding connections replaced. as with the exhaust process, the treatment

The other amino baths involved in the conversion process the amount of one necessary for residual crosslinking

or halohydrin ether compounds correspond to acid acceptors in the form of an alkali hydroxide, a

the alkali metal carbonates or bicarbonate or a salt mentioned in the main patent under a) or b)

ties. 20 from inorganic base and organic acid, both

To introduce the polysiloxane residues during the, for example, sodium acetate. The pH Particularly suitable for condensation are dimethyl liquor containing the acid acceptor polysiloxane derivatives with 5 to 10 or more silicon between 6 and 11 are. The exhaust process is Atoms, which continue to have reactive groups, do not matter whether the acid acceptor treats. Such groups are preferably allowed to take a bath before the treatment or during or Alkylene or arylene radicals bonded to silicon atoms after the condensation product has been absorbed to form 1,2-halohydrin and 1,2-halohydrin ether is set.

groups and reactive amino hydrogen atoms. The condensation products serve in particular

containing amino or polyamino groups. Those for treating synthetic or semi-synthetic

Polysiloxane derivatives can be one or more of the 30 textile materials, e.g. B. made of polyamides, polyesters,

contain reactive groups. Polyacrylonitrile, polyvinyl chloride, acetyizellulose and

Polysiloxane derivatives which resemble such groups, optionally in a mixture with natural

hold, are basically known and partly in borrowed fiber materials such as wool, silk or cellulose.

Commercially available. You can e.g. B. by reaction by drying the treated textile materials

of ammonia, amines or polyamines, the polycondensates turn into a high molecular weight,

knew halogen, epoxy or carboxyorgano- insoluble state. Drying can be done at

polysiloxanes, or by reaction of epi room temperature or below that in the textile industry

halohydrins, dihalohydrins or dihalohydrins customary conditions up to 200 ⁰ C carried out

hydrin ethers with hydroxy- or aminoorganopoly-, whereby the hardening time increases with

siloxanes produced by known methods 40 temperature drops,

be (cf. Noil, Chemie und Technologie der...

Silicones [1960], pp. 170/171). The preparation of the- Example 1

like connections is not claimed. A knitted fabric made of textured! Polyester continuous yarn

The condensation reaction for the production of the was carried out on a reel vat in a liquor

claimed condensation products is treated in a ratio of 1:30 with a liquor that is im

carried out in the manner described in the main patent, liter 1.5 g of the condensation described below

the degree of conversion by determining the sation product, 1.5 g of sodium acetate and 0.2 g

halogen ions or sodium carbonate formed during the reaction. Treatment was at

is controlled by the increase in viscosity. Carried out in the 6O ⁰ C for 20 minutes. Subsequently

Final product to 20 to 90%, preferably 50 50, the material was dewatered and at 80 to 100 ⁰ C.

about 80% of that in the starting compounds is present and dried.

those reactive amino or halohydrin The sample treated in this way would have reacted with one another together with ether groups. The remainder of an untreated sample of a chemical cleaning action comes to a standstill by itself with perchlorethylene and a commercially available cleaning agent when the pH falls below 7 or is terminated by acidification when the desired degree of conversion is reached together with men's suits. The reactants of an operational dry cleaning plant are thrown into such a large quantity. After cleaning, the treated ratio showed that the ratio of the sample had a whiteness of 98.5% compared with that of the amino hydrogen atoms to the untreated halohydrin sample. Both the chemically ether groups in the condensation product 1: 0.6 to 60 purified sample as well as a correspondingly from-1: 1.5 is. The total amount of lipophilic armed, 20 times residues with a commercially available home-hydrocarbon and Polysiloxanresten loading halt detergent at 40 ⁰ C washed sample had contributes about 2 to 65, preferably 6 to 30 wt very good antistatic properties,
percent of the total weight of the condensation product used for the equipment. With regard to the hardenability of the Kon-product was made as follows:
Densation products must comply with the conditions specified in the main patent. flasks fitted with a meter and a dropping funnel

The condensation products are presented from aqueous 318 g of diethylene glycol, 9 g of boron trifluoride

5 6

Acetic acid added the mixture is stirred (36% BF ₃₎ at 70 ° C. Subsequently, the tissue to a fleet and 558 g of epichlorohydrin was added dropwise so that the receiving squeezed out of 40 percent by weight and the reaction temperature by means of moderate external cooling to a tenter at 100 to 120 ⁰ C. dried, could be kept between 68 to 72 ° C and the sample was together with an untreated

then stirred for 30 minutes at about 7O ⁰ C. 5 Sample of a chemical cleaning with Perchlor-Afterwards 32 g tallow amine, 192 g of a linear ethylene and a commercial cleaning-built dimethylpolysiloxane derivative with finally together with men’s suits in a permanent primary aminopropyl group (molecular weight technical dry cleaning system, approx. 1000), 91 g of 50% strength sodium hydroxide solution and 50 g of iso- After cleaning, the treated sample had a propanol added, heated to 95 ° C. and stirred for 60 minutes at this whiteness of 102% compared to the untreated temperature. After rehearsal, on. The antistatic properties of the bekühlen at 8O ⁰ C were further 132g dipropylene treated sample were added both after multiple triamine, 1000 g of 50% isopropanol and 150 g of dry cleaning 20 times and after washing 50% sodium hydroxide solution. The reaction with a commercially available household detergent at mixture was stirred at 80 to 83 ° C so long 15 40 ⁰ C very good.

up to 62% of the organically bound chlorine had become ionogenic. The condensation used in the equipment had become. By adding 450 g of 30% strength product, the following was prepared:
Formic acid, a pH of from one under 5 Into the apparatus described at 70 ⁰ C

placed and stirred cold. It was a viscous in 88.5 g of diethylene glycol bischlorohydrin ether with 25.5 g Water readily soluble condensation product obtained. 20 of the aminopropyl dimethyl used in Example 1

polysiloxane derivatives, 9.1 g of 50% sodium hydroxide solution and

Example 2 5 g of 50% strength isopropanol are stirred up. The mixture

was implemented at 90 ^° C. for 75 minutes. On-..

Textured continuous polyester yarn, which was then dyed with a closing at 85 ° C 13.2 g dipropylenetriamine, disperse dye in a pink shade 25, 120 g 50% isopropanol and 15 g 50% sodium, was added to packages in the dyeing machine with caustic and at 85 ° C for so long, treated a liquor which had become 1.5 g per liter of the condensation product, 1.5 g, which was described below in an ionogenic manner, up to 63% of the organically bound chlorine. Finally, acetic acid was used to contain sodium acetate and 0.2 g of sodium carbonate. adjusted to a pH of 4.5. The liquor ratio was 1:20. After a loading 30 a clear viscous solution was obtained,
treatment time of 20 minutes at 6O ⁰ C. .

dehydrated and dried as usual. Example 4

From the finished part, the front part became a fabric made from a fabric in the presence of alkali

of a pullover was knitted, while the back part was slightly yellowing polyacrylonitrile fiber on a similarly colored, unfinished padder with a liquor that was produced per liter of 120 g of the nachPartie. After sewing the condensation product described below and the front and back parts together, the sweater containing 13.5 g of sodium acetate and which had been adjusted to pH 6 with 30% chemical cleaning together with a portion of acetic acid was subjected to normally soiled knitwear. After being equipped. Then, on about 50% Flott final purification showed the equipped front part 40 and squeezed receptive to the tenter no deterioration of the hue and sub dried at 120 ⁰ C.

was practically indistinguishable in appearance from the non-chemical cleaning in the presence of

equipped back part. No graying occurred on the items to be cleaned.

The condensation product was produced chemically as follows: The antistatic effect was found to be: 45 resistant to cleaning and washing.

In the apparatus described there were 408 g. The condensation product was as follows

technically pure triethylene glycol bischlorohydrin ether produced:

submitted, at 70 ⁰ C successively 32 g of coconut amine, in the described apparatus were at 75 ⁰ C

20.4 g of the aminopropyl used in Example 1, 177 g of diethylene glycol bischlorohydrin ether, 102 g of the dimethylpolysiloxane derivative, 36.5 g of 50% strength sodium hydroxide 50 used in Example 1 and 20 g of isopropanol were added to 95 ° C - siloxane derivatives, 34.5 g of 50% sodium hydroxide solution and warms, mixed at this temperature for 45 minutes after- 20 g of 50% isopropanol and stirred for 120 minutes and cooled to 80 ° C. The mixture was then subsequently stirred at 97.degree. Subsequently, at 53 g of dipropylenetriamine, 500 g of 50% isopropanol 70 ^° C., 21.2 g of dipropylenetriamine, 400 g of 50% iso- and 60 g of 50% sodium hydroxide solution were added. The mixed propanol and 20 g of 50% sodium hydroxide solution was heated to 85 ° C. and stirred for so long, and reacted at 85 ° C. until 70% of the organically bound chlorine was 57% of the organically bound chlorine in ionically bound chlorine the ionic form had passed. In conclusion, 10% was gone. The reaction hydrochloric acid was then adjusted to a pH below 5. mix with dilute formic acid to pH 5.2

60 set.
Example 3 Example 5

An undyed fabric made of polyacrylonitrile fibers, polyacrylonitrile high-bulk yarn, was placed on a

was treated with a liquor on the foulard, the yarn dyeing machine (hanging system) was bulky,

which bleaches 100 g per liter of the 65 described below and then at a liquor ratio of

Condensation product, 20 g of sodium bicarbonate and 1:60 treated with an aqueous solution in the

1 g of a non-ionic wetting agent, for example 0.7 g per liter of the condensation described in Example 1

the basis of a fatty alcohol polyglycol ether. cation product and 0.3 g sodium carbonate

7 8

held. The treatment was carried out at 60 ^° C. for 20 minutes and the back part of the sweater was carried out together with long. Thereafter, the yarn was spun without a lot particularly heavily soiled men's intermediate rinsing and at 100 to 120 ⁰ C suits dry cleaned. After cleaning, it was dried in a hanging dryer. the finished sample has a whiteness of 107%,

From the finished part, the front part 5 was based on the degree of whiteness of the unfinished

knitted of a sweater while the back part is sample on. The finished sweater parts showed

from a similar, unfinished section, very good antistatic properties after cleaning

was produced. After sewing together the front properties.

and back part, the sweater was made together with other condensation products that are

a batch of men's suits of a chemical cleaners type for finishing textile material

subject to. After cleaning showed that can be used, you can as follows

equipped front part no graying and produce:

hardly differed in appearance from A) 115 g are obtained in the apparatus described

unequipped back part. an amidopolyamine-organopolysiloxane derivative with

... is 50 g of raw diethylene glycol bischlorohydrin ether

T he game 6 ■ mixed, heated to 8O ⁰ C and after adding

Polyamide carpet flakes were made with a liquor, 14 g of 50% sodium hydroxide solution and 350 g of 50% iso-

the 100 g per liter of the propanol described below is stirred at 85 ° C until 60%

Condensation product and 10 g of sodium bicarden of organically bound chlorine become ionic

bonat, after the dip-spin process 20 are. The reaction mixture is then with

equipped, centrifuged to 30% liquor uptake- glacial acetic acid adjusted to a pH value of below 5,

modified and dried in the usual way. The amidopolyamine - organopolysiloxane derivative

The sample was produced together with a sample that was not processed by reacting molar amounts after sewing into a gauze bag a linearly built, terminal carboxy together with a portion of normally soiled 25 alkyl group-containing dimethylpolysiloxane (Mol men's suits chemically cleaned. The equipped weight about 1000) with dipropylenetriamine.
Sample showed compared to the unfinished sample B) In the apparatus described, 65 g of a β- hydroxypropylpolyamine-dimethylpolysi were only barely detectable, while the antistatic effect after the chemical loxane derivative was cleaned with 105 g of the bischlorohydrin ether, as also after several wet washes 30 of an adduct of 3 moles of ethylene oxide, a common household detergent, was good. of glycerine in the presence of 24 g of 50% sodium

The condensation product was leached as follows and 375 g of 50% isopropanol at 95 ° C

posed: implemented until 55% of the organically bound

In the apparatus described, 235 g of chlorine became ionic. Then will

a bis-chlorohydrin ether-polysiloxane derivative previously adjusted to pH 3.5 with 10% hydrochloric acid,

placed, at 85 ° C with 9.6 g of di-hexamethylene triamine, The β - hydroxypropyl polyamine - dimethylpolysil-

600 g of 50% isopropanol and 10 g of 50% oxane derivative was produced by reacting mo-

Sodium hydroxide solution ^{reacted at 90 0} C until 55% larer amounts of a 1,2-epoxypropyl-dimethylpoly-

of the organically bound chlorine in the ionic siloxane (molecular weight about 500) with triethylenetetramine.

Form had passed. Then with 40 C) In a stirred autoclave to 500 g

60% acetic acid adjusted to pH 4.5. . one containing linear phenolic groups

The aforementioned bis-chlorohydrin ether-polysiloxane-dimethylpolysiloxane derivative (molecular weight about 500)

derivative was added by the addition of 3 moles of ethylene- 88 g of ethylene oxide and the resulting

oxide to 1 mole of a slightly branched dimethyl adduct by subsequent reaction with 93 g

polysiloxane compound with 3 to 4 terminal 45 epichlorohydrin into the corresponding y-chloro-jS-hy-

primary hydroxypropyl groups (molar weight about converted hydroxypropyl ether derivative. 136.5 g of this

2000) and subsequent reaction with 2 mol of epi product are then added with 26.4 g of dipro-

obtained chlorohydrin. pylenetriamine and 17 g of 50% sodium hydroxide solution and

. ₁₇ furthermore 100 g of ethylene glycol bischlorohydrin ether in

ü e 1 s ρ 1 e 1 7 _g0 Presence of 400 g of 50% isopropanol and 40 g

A cream-colored, already bulked polyacrylic 50% sodium hydroxide solution, if converted, up to 67%

Nitrile high-loft yarn has become ionic on a yarn dye of organically bound chlorine

apparatus in a liquor ratio of 1:60 with one. It is then adjusted to a pH value below

treated aqueous liquor, the 0.7 g per liter of the 4.7 set.

Example 4 described condensation product so- 55 D) 0.3 g of sodium carbonate are contained in a closed stirred autoclave. The equipment was 170 g Triäthylenglykolbischlorhydrinäther together carried out for 20 minutes at 6O ⁰ C. Arrival with 25.5 g of Aminoschließend used in Example 1, the yarn without intermediate rinsing propyl-dimethylpolysiloxanderivates, 20 g of 25% was purified and spun at 100 to 120 ⁰ C in the festoon ammonia and 50 g of 50% sodium hydroxide solution in counter-dried. 60 of 150 g of 50% isopropanol was so long at about

From the finished part, the front part was converted at 100 ^° C., up to 55% of the organically bound

of a sweater, while the back part has become chlorine ionic. Then with

diluted 10% acetic acid from a similar unfinished batch, with one weak

was produced. After sewing together the anterior acid, highly viscous solution is obtained.

Claims (1)

Patent claims: 1. Use of water-soluble or in. Water-dispersible curable condensation products that are bound to amino nitrogen atoms Hydrogen atoms and halohydrin ether groups in a ratio of 1: 0.6 to 1: 1.5 and contain lipophilic radicals with at least 8 carbon atoms and which are produced by Condensation of a) ammonia and / or primary monoamines and / or at least two amino hydrogen atoms containing polyamines and b) Di- and / or polyhalohydrin ethers of di- and polyalcohols having 2 to 6 carbon atoms and / or the addition products of 1 to 2 moles of alkylene oxide, preferably ethylene oxide, with these alcohols, wherein at least one of the reacting components is wholly or partly due to the lipophilic Radicals is substituted and where the amino or halohydrin ether groups of the starting compounds to 20 to 90%, preferably 50 to 70% have responded,