DE1935499A1 - Softeners - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG 1935499

Our reference: 0.Z. 26 279 Rt / Ot

6700 Ludwigshafen, July 11, 1969

Softeners

It is common practice to finish textile fiber material, i. E. to give it a soft feel by treating it with certain substances. The agents customary for this purpose usually contain long-chain alkyl radicals and a group that makes them water-soluble or makes it dispersible in water.

The finishing is done for various reasons, on the one hand, to facilitate the processing of fibers, tow, slivers, threads, yarns and other semi-finished textile products, by applying the fatty alkyl compounds both reduce the surface friction and make the fibers or their derivatives more supple, and thus optimal conditions for processing such as carding, carding, converting, combing, drawing, spinning, weaving, rewinding, Twisting, knitting and assembling, on the other hand, to create a soft, pleasant feel for finished textile products To generate grip and thus to favorably influence the character of the goods. Also serve to soften and increase the Elasticity in textiles in use helps to improve the wearing comfort and to make the material easier to care for do. This special form of finishing is usually carried out by the textile consumer himself as a post-wash treatment

It is known to use substances of the formula for the purposes mentioned

- C - _{O - CH 2} - CH ₂ ) ₂ NH-R ₂ -OHl X

- OH

679/66 009 883/223 *

- 2 - 0.Z. 26 279

to be used in which R _{1 is} a relatively long-chain aliphatic radical, R _{2 is} a low molecular weight alkylene group and X * is an anion. It has been found, however, that these substances only have a moderate softening effect.

New substances have now been found which, despite the related chemical structure, have a significantly better softening effect have known substances as the mentioned. The new substances correspond to the general formula

(R ₁ -C-0-A-) ₂ H ^ ² I «3

e X

in which R _{1 is} an aliphatic hydrocarbon radical ait II up to 17 carbon atoms, R _{2 is} a low molecular weight alkyl, cycloalkyl or hydroxyalkyl radical, R is a low molecular weight alkyl, cycloalkyl, hydroxyalkyl radical or a radical

j?

of the formula R ₁ -COA-, A is an aliphatic hydrocarbon radical having 2 to 6 carbon atoms, X * is the part of an acid anion corresponding to an elementary charge.

Of particular importance are those substances of the general formula which have _{a methyl group as the R 2} substituent and an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms or a cyclohexyl radical as the substituent R.

Examples of substances according to the invention are those of the following formulas:

./ ^H 3 (C ₄ , H "-C0-0-CH ₂ -CH ₂ ) ₂ Hx

vJH-r

Ί7

e 0 SO CH ₃ I.

(C ₁₇ H ₃₅ -CO-O-CH ₂ -CH ₂ ) Ji-CH ₃ I 0 SO ₃ CH ₃ II

O / ^CH 3

0 SO ₃ CH ₃ III

009883/2234

3 -
' CH _P -CH _P -OH

O.Z. 26 279

ση nil JV

I ³ · / 3

(C ₁₇ II, _r -C0-0-CH-CIU) ₃ N

Ό SO ₃ CH ₃

* 0 SO ₃ CH ₃

VI

The substances of the general formula can be used according to known Processes are produced, for example by transesterification of esters of longer-chain fatty acids with amines, which at least two hydroxyalkyl groups contain »and subsequent quaternization of the intermediates.

The new fabrics according to the present invention are outstandingly suitable for the finishing of textile fibers, for example those made of synthetic fibers such as polyester, acrylonitrile polymer and polyamide fibers, and in particular those which contain or consist of cellulose or regenerated cellulose fibers. They are mainly characterized by the fact that
they give excellent finishing effects with very simple application.

The application is carried out in the usual manner for finishing agents; so you can, for example, the textile material with the aqueous solutions of the compounds in concentrations either from 0.1 to
15 g / l from a long liquor or from 5 to 30 g / l from a short one
Treat liquor (foulard), it is expedient to work in an acidic, neutral or weakly alkaline medium, preferably in the pH range from k to 8. Without having to make further manipulations, you can then centrifuging the material or squeezing off and drying normally at 80 to 90 ⁰ C. However, the substances according to the invention can also be used together with other textile treatment agents, for example with agents for high-end finishing, such as dimethylolurea . Dimethylol propylene cder
ethylene urea or dimethylolglyo-al'rcnourein, a η ν; en- :; en.

0 P QgP 1 ι? ": ■ 'ii""■

ßAD ORK3IHAL

- 4 - O.Z. ? 6? 79

The application conditions customary for these known agents can be retained without further ado. The use of the new substances for wet laundry treatment is of particular importance. The fabrics are added to the last rinsing bath in a concentration of 0.02 to 0.5 % after the textile has been washed.

The substances of the general formula can be used alone or together with other auxiliaries; are mentioned in this Connection, for example, means for influencing the handle, for adjusting the viscosity and the pH value and for increasing it the cold stability, such as di-alkyl-dimethyl-ammonium chloride and sulfate, fatty alcohol oxyethylates, alkyl and dialkylphenol oxyethylates, Fatty acid oxyethylates, polyglycols, polyglycol ethers, Electrolytes such as calcium chloride, sodium chloride, magnesium chloride, organic complexing agents such as the salts of nitrilotriacetic acid, the dioxäthylaminoacetic acid, the ethylenediaminotetraacetic acid, the Oxäthyläthylendian.inotriessigsäure and the diethylenetriaminopentaacetic acid, organic phosphonic acids and solvents such as isopropanol and ethanol.

The parts and percentages given in the examples are weight units.

example 1

Product of formula I.

a) 596 parts of methyl stearate, 119 parts of N-methyl-N, N-diethanolamine and 7 parts of aluminum isopropoxide are refluxed for four hours under a nitrogen atmosphere. After the boiling point of methanol is reached, 58.5 parts of methanol are distilled off for six hours, with the pot temperature rises to 220 ⁰ C. This gives a colorless, solidifying melt, which is recrystallized from ethanol. Yield 590 parts (= 90.5 % of theory ), melting point 40-4l ° C.

b) 195 parts of N-methyl-N ₅ N-di (bis-ß-stearato) ethylamine and 10 parts of methyl glycol are heated to 60 ° C. with stirring and 36 parts of dimethyl sulfate are added dropwise at this temperature. After three hours of stirring, colorless crystals which are readily soluble in water are obtained. Yield: 230 parts (= 98.0 % of theory), N, N-dimethyl

009883/2234. - 5 -

N, N-di (ß-stearato-ethyl) ammonium methosulphate with a melting point of 118-119 ⁰ C.

Example 2

Product of formula II

a) 447 parts of methyl stearate, 74.5 parts of triethanolamine and 5.1 parts of aluminum isopropoxide are, as described in Example 1, reacted. 45 parts of methanol are distilled off in six hours, the temperature in the reaction flask rising to 212 ° C. This gives 470 parts (= 98.5% d. Th.) N-tri (beta-stearato-ethyl) amine as colorless crystals of melting point 44-45 ⁰ C

b) 237 parts of N-tri (beta-stearato-ethyl) -amine, as described in Example 1, is reacted with 31.5 parts of dimethyl sulfate at 8O ⁰ C in 27 parts of methyl glycol. 257 parts (= 95.9 % of theory) of N-methyl-N-tri (β-stearato-ethyl) ammonium methosulfate with a melting point of 49-51 ° C. are obtained.

Example 3

Product of formula III

a) 295 parts of methyl stearate, 93 parts of cyclohexyldiethanolamine and 4 parts of aluminum isopropoxide are, as described in Example 1, reacted. 40 parts of methanol are distilled off over the course of five hours, the temperature in the flask rising to 260.degree. Yield 350 parts (97.3 % of theory ) of N-cyclohexyl-N, N-di (β-stearato-ethyl) amine;

n ⁵⁰ = 1.4589
D.

b) 216 parts of N-cyclohexyl-N, N-di (ß-stearato-äthyDamin and 25 parts of methyl glycol is mixed at 8O ⁰ C with 38 parts of dimethyl sulfate. After four hours of stirring, giving 250 parts (= 98.4% d. Th .) N-Methyl-N-Cyclohexyl-N, N-di (ß-stearato-ethyl) -ammonium-methosulphate as a melt. Melting point: 43-45 ° C.

- 6 009883/2234

Example 4

Product of formula IV

a) 298 parts of methyl stearate, 74.5 parts of triethanolamine and 3.7 parts of aluminum isopropoxide are, as described in Example 1, reacted. 30 parts of methanol are distilled off in 21/2 hours, the temperature in the reaction flask rising ^{to 212 ° C.} 335 parts (= 98.6 % of theory ) of H-jä-hydroxyethyl-N, N-di (β-stearato-ethyl) amine with a melting point of 44-45 ° C. are obtained

b) 224 parts of N-ß-hydroxyethyl-N, N-di- (ß-stearato ~ ethyl) -ard; _; and 26 parts of methyl glycol are methylated at 8O ⁰ C with 41.5 parts of dimethyl sulfate as described in Example. 1 260 parts (= 98.1 % of theory ) of N-methyl-N-β-hydroxyethyl-N ^ II-di- (β-stearato-ethyl) ammonium methosulfate are obtained in the form of colorless crystals with a melting point of 72 -75 ° C.

Example 5

Formula V product

a) 551 parts of methyl stearate, 149 parts of U-butyl-N, N-diethanolamine and 6.8 parts of aluminum isopropylate are refluxed for five hours under a nitrogen atmosphere and 57 parts of methanol are distilled off over a further six hours. 634 parts (= 91.5 % of theory ) of N-butyl-N, N-di (ß stearato-ethyDamine with a melting point of 30-3 ° C. are obtained.

b) To 216 parts of N-butyl-N, N-di (β-stearato-ethyl) ainine and 21 parts of methyl glycol, 37.8 parts of dimethyl sulfate are added dropwise at 50.degree. 250 parts (* 98.8 % of theory ) of N-methyl-M-butyl-N, N-di (β-stearato-ethyl) ammonium methosulfate are obtained as colorless crystals with a melting point of 145-153 ° C.

Example 6

Product of formula VI

a) 298 parts of methyl stearate, 124 parts of N-n-butyl-II, I-diisopropanolamine and 5 parts of aluminum isopropylate v / erd ^ n, such as

009883/223 / »- '' -

BAD ORKSINAt

O.Z. ? 6 279

described under Example 1, implemented. After 37 parts of methanol have been distilled off, the temperature in the reaction flask rising to 260 ° C., 389 parts of N-n-butyl-N, N-di (β-stearato-isopropyl) amine are obtained as a light yellow melt.

⁵⁰ =

= 1 _f

b) 26 parts of Nn-butyl-N, N-di (β-stearato-isopropyl) amine are methylated at 75 ° C. with 3 parts of dimethyl sulfate, as described in Example 1. 2 ^ 5 parts (= 96.4 % of theory ) of Nn-butyl-N, N-di (β-stearato-isopropyl) ammonium methosulfate are obtained as

light brown melt.
50

(C ₁₇ H
^7th

Example 7

.COO-CH-CH ₂ ) ₂ - * U CH ₃

OSO ₃ CH ₃

a) 296 parts of methyl stearate, 95 parts of triisopropanolamine and 3.9 parts of aluminum isopropoxide are, as described in Example 1, reacted. 30 parts of methanol are distilled off in four hours, the temperature in the reaction flask rising to 231 ° C. 350 parts (= 97.8 % of theory ) of li-isopropanol-N, N-di (β-stearato-isopropyl) amine are obtained. Melting point 3 * J C.

b) 217 parts of N-isopropanol-N, li-di (ß-stearato-isopropyl) amine are methylated with 38 parts of dimethyl sulfate at 80-90 ° C. 250 parts (= 98.0 % of theory ) of N-methyl-N-isopropanol-ΐΓ, Ν-di (ß-stearato-isopropyl) ammonium methosulphate are obtained in the form of pale yellow crystals with a melting point of 52-53 ° C.

Example 8

CH-

00 9 88 3/223

OSO

SAD

- 8 - OZ 26 279

a) 298 parts of methyl stearate, 103 parts of N-methyl-N, N-di-isopropanolamine and 4 parts of aluminum isopropoxide are reacted analogously to Example 1. 54 parts of methanol are distilled off in 6 hours, the temperature in the reaction flask having risen to 260.degree. 338 parts (= 98.3 % of theory ) of N-methyl-N, N-di (β-stearato-isopropyl) amine are obtained.

b) 204 parts of N-methyl-N, N-di (β-stearato-isopropyl) amine are methylated with 38 parts of dimethyl sulfate at 70 ° C., as described in Example 1. 237 parts (= 97.9 % of theory ) of N, N-dimethyl-N, N-di (β-stearato-isopropyl) ammonium methosulfate with a melting point of 47 ° C. are obtained.

Example 9

CH

V4t

4h,

OSO ₃ CH ₃

a) 298 parts of methyl stearate, 110 parts of N-ethyl-N, N-di-isopropanolamine and 6 parts of aluminum isopropoxide are reacted analogously to Example 1. 39 parts of methanol are distilled off in 7 hours, the temperature in the reaction flask rising to 250 ° C. 3 ¹ JO parts (= 97.2 % of theory) of N-ethyl-N, N-di (ß-stearato-isopropy-amine) are obtained.

n ⁵⁰ = 1.4478
D.

b) 208 parts of N-ethyl-N, N-di (ß-stearato-isopropyDamin and 38 parts of dimethyl sulfate at 75 ⁰ C as described in Example 1, is reacted. This gives 233 parts (= 96.2% d. Th .) N-methyl-N-ethyl-N, N- (di-ß-stearato-isopropyl) ammonium methosulfate,

n ⁵⁰ = 1.4551
D.

Example 10

(CH ₃ (CH ₂ ) ₇ CH * CH- (CH ₂ ) ₇ -COO-CH-CH ₂ ) _? -N,

CH.

009883/2234

/ ^CH 3

, -CH-OH

OSO ₃ CH ₃ *

-Q-

- 9 - O.Z. 26 279

a) 74 l parts of methyl acid ester, 238 parts of triisopropanolamine and 10.3 parts of aluminum isopropoxide are reacted analogously to Example 1. In 5 hours and 81 parts of methanol are distilled off, the temperature rising in the reaction flask at 22O ⁰ C. 798 parts (= 92.2 % of theory ) of N-isopropyl-N, N-di- (β-oleatoisopropyljamine) are obtained as a brown oil.

n ²⁰ = 1.4698
D.

b) 216 parts of N-isopropyl-N, N-di (ß-oleato-isopropyl) amine

reacted at 7O ⁰ C according to Example 1 with 35 parts of dimethyl sulfate. 245 parts (= 95.7 % of theory ) of N-methyl-N-isopropyl-N, N-di (β-oleato-isopropyl) ammonium methosulfate are obtained as a brown oil.

on
ir ^u = 1.4709

Example 11

Cotton tricot fabric was made at 95 ° C. in a liquor ratio of 1: 6 Washed in a drum washing machine with a commercial heavy duty detergent.

1 g / l of an oily solution of the compound was added to the last rinsing bath of formula I added.

After being spun off and dried, the textile material had a pleasant, soft and puffy feel.

Example 12

Terry towels made of cotton were ^{washed at 90 °} C. and a liquor ratio of 1:10.

1 g / l of a laundry aftertreatment agent was added to the last rinse bath admittedly that

6 % of the compound of formula IV and
1 % stearic acid decaglycol ester

contained.

009883/2234 -10-

- 10 - O.Z. ? 6 279

By adding the stearic acid polyglycol ester, the handle and the absorbency of the terry towels could be further improved increase.

Example 13

Cotton articles were ^{washed at 85 °} C. in a drum washing machine with a liquor ratio of 1:15.

1 g / l of a laundry treatment agent was added to the last rinse. consisting of ... .

6.5 % of the compound of formula V and

0.5? a reaction product of oleyl alcohol with the 12-fold molar amount of ethylene oxide

added.

After being spun off and dried, the textile material had a pleasing soft handle.

Example 1 *>

Cotton cheeses were, after bleaching and rinsing on the packing apparatus at a liquor ratio 1: 10 with the aqueous solution of 0.5 g / l of the compound of formula III at pH 6 for 15 minutes at 45 ⁰ C treated, centrifuged and dried.

The yarn treated in this way is soft and slippery, so that it behaves properly in subsequent processing such as rewinding, twisting, warping and weaving, i.e. the number of thread breaks is reduced and the yarn appearance is not adversely affected by the mechanical influences.

Finished products made from yarns made in accordance with the foregoing treated, are characterized by a pleasantly soft and voluminous handle.

009883/2234 _ '_

- 11 - O.Z. 26 279

Example 15

Polyaerylnitril-bulk yarn, after staining with 0.5 g / l of a compound of formula V in a liquor ratio 1: 8 for 10 minutes at ⁰ ^ 5 C and a pH of 5-6 treated. After centrifuging and drying at 80-100 ° C, the result is a soft, fluffy yarn that can be processed further without any problems. The finished products made from this yarn treated in this way are characterized by a pleasant, soft and puffy handle.

Q09883 / 223A

- 12 -

Claims (2)

Claims substances of the general formula ( _Rl -i-0-A-) ₂ R atic hydrocarbon residue with 11 in the R ₁ an alipl
up to 17 carbon atoms, R _{2 is} a low molecular weight alkyl, cycloalkyl or hydroxyalkyl radical, R is a low molecular weight alkyl, cycloalkyl, hydroxyalkyl radical or a radical of the formula R ₁ -SOA-, A is an aliphatic hydrocarbon radical with 2 to 6 carbon atoms, X is the part of an acid anion corresponding to an elementary charge. 2. Use of the substances according to claim 1 sum finishing of textile fiber material. Badische Anilin- ft Soda-Fabrik AO 009883 / 223A