DE1930768A1 - Process for the permanent finishing of textile materials containing cellulose fibers - Google Patents

Description

Patent department Düsseldorf, 9.6.1969

Dr. Bz / Pm. Henkelstrasse 67

Patent application.

D 3720

"Process for the permanent finishing of textile materials containing cellulose fibers" .

The invention relates to a method for permanent finishing of textile materials containing cellulose fibers with the aim of eliminating those that occur when washing such textiles Prevent hardening.

It is known that unpleasant hardening occurs when textile materials containing cellulose fibers are washed. It has therefore already been proposed either to add compounds with a softening effect to the detergents or else the textile materials after washing with a softener containing rinsing bath to treat. The disadvantage of the means used is, however, their lack of ' Resistance to washing, so that the treatment has to be repeated over and over again.

It is also known that cellulose fabric, with dyes, which contain reactive hydrogen atoms, Can be dye or print washfast if the treatment is carried out in the presence of a bis-acryloyl-alkylenediamine and alkaline acting means performs.

The invention relates to a method for permanent finishing of textile materials containing cellulose fibers, which is characterized in that the textile material in the presence of alkaline agents with solutions or dispersions of compounds of the general formula

009882/2052

A) CH ₂ = CH-CO-NH-CH ₂ - NH-CO-CH = CH ₂ , or

ClCH ₂ -CH ₂ -CO-NH- CH ₃ -

where ή is an integer from 1 to β,

and '

B) R ₁ -XH,

wherein R _{1 is} an alkyl radical optionally interrupted by 0 atoms or -CÖNH groups and having 16 to 36 carbon atoms,

X = -NH-, -NR ₂ -, -0- or -S- and Rp denote an alkyl radical with 1 to 24 carbon atoms which is optionally interrupted by O atoms and / or substituted by hydroxyl groups, the radicals R ₁ and Rp together do not contain more than 36 carbon atoms,

where the molar ratio of compounds A): B) is approximately 1i5 is 2.5: 1,

-behandelt, dried and fixed at temperatures above 100 ^0C.

The claimed process achieves a permanent softening effect, even after numerous washes is not lost in washing machines with commercially available detergents. The hardening of the textiles through repeated washing can thus be practically completely prevented.

The compounds of the general formula A) are known, for example, from DAS 1 155 Ο88 and are not claimed as such. They are obtained by reacting 2 moles of acrylic acid chloride or S-chloropropionic acid chloride with; 1 mole each of a diamine, such as, for example, styleridiamine, propylenediamine, butylediamine and hexamethylenediamine. Particularly suitable as a connection _? fe ^ ii ^ · -; 00/98 82/2052: - \ "■ '. ■ ^. 3 -:

dung Λ) is NjN'Bisacryloyl-methylenediamine, which is produced by condensation of ?. Mole of acrylamide with 1 mole of formaldehyde can be obtained.

Suitable agents of group B) are primarily higher primary or secondary alkylamines which contain at least one alkyl rust with 16 to 2 ^l \ C-ftomen. Examples of compounds of this type are hexadecylamine, octadecylamine, docosylamine and amine mixtures, such as are obtained by converting natural fats and oils, e.g. tallow fats, also oleylamine, tallowoxypropylamine, N-methyl-octadecylamine, dioctadocylamine and N- ( 2,3-Dihydroxypropyl) octadecylamine, also acylation products of di- and polyamines with higher fatty acids of chain lengths C ^ g to C ^^, such as N-Steärpyl- "ethylenediamine or N-Palrr.itoyl-N ¹ - (3- hydroxy'ithyl) -äthylendlamine-, other suitable compounds are higher fatty alcohols with HS up to J \ C atoms as well as the hydration products produced from such fatty alcohols by the Guerbet reaction ir.it Ί up to J> 6 C atoms Examples of these are hexadecyl alcohol, octndeeyl alcohol, and also the fatty alcohols or fatty alcohol compounds derived from natural fats or oils, corresponding to chain lengths, for example cleyl alcohol, behenyl alcohol and tallow alcohol, and that made from tallow alcohol by Guerbet reagent Diireri ^ ation product obtained by action. In addition, higher alkyl mercaptans with 16 to 2k carbon atoms, such as hexadecyl mercaptan and octadecyl mercaptan, can also be used. Finally, the Anlagerun _{ 'come sprodukte of up to h moles of an alkylene oxide, in particular nthylenoxid Propylenoxld, Glycl, d or Glycerinchlorhydrin to the aforementioned Alkylarr.ine, fatty alcohols or Alkylir.ercaptane into consideration.

The reaction of the alleylenediamine derivatives mentioned under A) with the cellulose fiber bzv :. with the. Group B compounds) is accelerated by catalytically active alkaline agents.

0 0 9882/2052

BATH ORIGINAL

Alkali hydroxides such as sodium hydroxide are preferably used as such or potassium hydroxide and quaternary ammonium hydroxides such as tetraethylammonium hydroxide into consideration. Of the The pH value of the treatment solutions should be above pH 1.1.

To carry out the claimed method, the equipment to be equipped Textile materials with solutions or dispersions of compounds A) and B) treated. Typically, the finishing is done in a single bath that connects the A) and B) together. However, you can also use two work in separate bathrooms. Another variation of the way of working consists in that the textiles before the actual finishing with an aqueous or alcoholic solution that contains only the alkaline catalyst, be pretreated, or that one after application of the solution of the compounds A) and B) after-treated with such a catalyst solution. The molar ratio of compounds A): B) should be approximate 1 * 5 - 2.5 i 1, preferably 2: 1.

Suitable solvents for carrying out the process are primarily lower aliphatic alcohols with 1 to 4 carbon atoms or water, as well as mixtures of these alcohols with Water. Suitable alcohols are, for example, methanol, ethanol and isopropanol. Hardly soluble compounds can also be used The help of emulsifiers, such as higher alkyl sulfates, alkyl ether sulfates, Alkyl sulfonates, alkyl aryl sulfonates or addition products from alkylene oxides to higher fatty alcohols or alkylphenols, dispersed and used in this form will. Conversely, the use of emulsifiers makes it possible to increase or decrease the alcohol content of the treatment liquor to reduce less and possibly to use pure water as a solvent.

■■■■■■■■■■ ■; ■, .- ■ '- ^; ... V -'- "-5> .y:

009832/2052: - '. . '

The treatment of the textile materials is carried out at about room temperature and takes a treatment time of 5 to 60 minutes. The solutions used should each contain about 5 to 100 g / l of compounds A) and B). The treatment is carried out in the usual way, for example on the poulard or by spraying. Following the equipment is thrown off to a remaining-liquor content of 100 to 400% or squeezed and at temperatures up to about 100 ⁰ C, optionally with application of vacuum, pre-dried, then heat treatment is from about 1 to 6o minutes duration at temperatures of above 100 ° C., preferably 120 to 160 ° C., the compounds A) and B) being fixed on the textile material so as to be washable. The treated textiles have a full, soft feel that is not lost even after numerous washes, such as those carried out in the household using washing machines and commercially available coarse or fine detergents.

009 8 82/20 52

; ■■■ - 6 - ■ -.

Example 1:

Extracted cotton terry cloth was immersed in a solution of 30.8 g (0.2 mol) of N, N ¹ -bisacryloylmethylene diamine, 26.9 β (0.1 mol) of octadecylamine and 10 g of sodium hydroxide in 2 liters of methanol for 15 minutes. After dripping off, it was pre-dried in the air and then fixed at 1.20 ^° C. for J> 0 minutes. .

To demonstrate the equipment properties achieved the fabric is subjected to the following washing treatment:

The finished fabric was washed in the presence of clean carrier fabric in a drum washing machine 15 times with a commercially available coarse detergent (dosage 4.0 g'l, liquor ratio 1: 12.5) in the boil cycle (max. Temperature 95 ° ^). Each wash cycle consisted of a main wash and 5 rinses. After the 1st, 5th, 6th, 9th, 12th and 15th wash, a gelatinous sample was taken and, after drying, several experienced persons (5 to 7) assessed the feel of these samples, with grades from .

1 = full and very soft handle, up to

■ "■■ .- ■ ■■". "■■■■■

5 = very hard grip

were awarded. The individual assessments each became the mean values are calculated. The following results were obtained obtain:

Number of washes 1 3 69 12 I5 Handle 1.0 1.0 1.0 1.0 1.1 1,>

For comparison, a cotton terry fabric of the same type, which was not subjected to the finishing described above, was washed and assessed in the same way. Therefor

- ": ■■ ■. ' ■ ': ■■■■■■; \'. ■:. ■ '.'. ■ ■ '- , - 7 - ^:

* 009882/2052 - ^ ORiGfNAL

1330768

- 7 the following grips were determined:

Number of washes 1 3 6 9 12 15 Handle 2.3 2.4 2.8 3.1 3.4 4.0

While the original terry cloth through the washing treatment hardened, the fabric treated by the method according to the invention still showed a full and even after 15 washes soft grip.

Example 2;

Pieces of cotton terry were, as described in Example 1, with a solution of 30.8 g (0.2 mol) of N, N ¹ -bisacryloyl-methylenediair.in and 0.1 mol of a compound of group B) in 2 liters of methanol treated. After draining and air drying, the tissue pieces were fixed for 30 minutes at 12O ⁰ C.

The finished fabric pieces were, as indicated in Example 1, washed and checked. The examinations showed excellent in all cases, even after 9 and 15 V. Handle notes.

Component B used. Reach for η washes

Quantity (g) 1 3 69 12 15

n) Tallow amine (C ₁₆ -C ₁₈ ) 25.9 1.4 1.4 - 1/6 -

b) Dodecyloxypropylamine 24.6 1.5 1.5 - 2.0 -

c) Octadecyloxypropyl-amine 32.8 1.0 1.0-1.6

d) Tallowpxypropylamine 31.6 1.5 1.5-2.0

e) N-methyl-octadecyl- '28.4 1.0 1.0-1.9 amine ...-. . ■

00 98S2 / 2Q52

BATH ORIGINAL

1330768

Component B

- 8th-

eihges. Amount (g)

Reach for η washing
3 6 9 12 15

f) Dioctadecylamine 52.2

g) N-3-tearoyl-32.6 ethylenediamine

^h ) N-palmitoyl-N ¹ -

(ß-hydroxyethyl) - 53.2 ethylenediamine

i) N- (2,3-dihydroxy-

propyl) -octadecyl- j5 ^ - # 4 amine

k) C, _o / C, ^ - Guerbet- 52.8 ^ ^ ⁰ alcohol

Γ) Hexadecylniercaptan 25/8

1.5 1.5 1.5 1.8 2.0 2.0 1.8 1.8 1.9 2.3 2.4 2.4

2.0 2.0 2.1 2.1 2.3 2.4

1.5 1.5

1.8

1.4 1.8 1.8 2.0 2.0 2.0

1.3 1.8 2.0 2.0 2.0 2.0

Example 3:

Using 7g of an emulsifier would result in a dispersion of 30.8 g (0.2 mol) bisacryloyl methylenediamine, 26.9 g (0.1 mol) Octadecylamine and 10 g of potassium hydroxide in 1.9 l of water and 0.1 1 isopropanol produced.

Baurmiollfrotteegewebestücke were immersed for 15 minutes in this solution, squeezed, vprgetroctoet 4 hours at 50 ^o C and then fixed for 30 minutes at 120 ° C. The washing treatment and handling as carried out in Example 1 led to the following result: =

0 09882/2052

Emulsifier handle after η washing

1 3 6 9 12 15

a) Nonylphenol + 9.5 moles 1.3 1.4 1.5 1.8 1.9 2.0 Ethylene oxide

b) fatty alcohol-C ^ - ^ - ¹ »° ¹ O 1.5 2, G 2.0 2.0

diglycol ether sulfate sodium salt (27 #)

c) - "- 1.0 1.3 1.5 2.0 .2.0 2.3

Example 4;

Cotton terry cloth fabric was immersed in a hot solution of 15.4 g (0.1 mol) of bisacryloylmethylene diamine and 13.4 g (0.05 mol) of octadecylamine in 700 ml of methanol for 15 minutes. After 6 hours of intermediate drying at 50 ° C., the fabric was immersed in a solution of β g of sodium hydroxide in 700 ml of methanol, dried for 2 hours at 50 ° C. and then fixed at 120 ° C. for 30 minutes. , _; ·

The washing treatment and handle grading carried out as in Example 1 led to the following result:

Number of washes 1 3 9 Handle 1.0 1.0 1.4

example 5 '

Cotton terry fabric was finished as in Example k , but the order of the finishing baths was reversed, ie it was first treated with a solution of 6 g of sodium hydroxide in 700 ml of methanol and then after / Iwlseheiiti'oii with a solution of 1-5.4 g of bisacryloyl methylenediarain and 13.4 g of octadecylamine in methanol.

009882/2052 '-.10. »

133 07 6

ν. . ■■■ '■■: - ν ...' ■. : - ίο - .- ■■■ -; ... ■ -. ■■ ■■; ■■■. -;.

After the washing treatment, the following assessment was made:

Number of washes 1 3 9

Handle 1.3 1> 3 V5

Example 6:

Cotton terry fabric was dissolved in a solution of 10 g of soda | hydroxide immersed in 1 liter of water and ^{intermediate drying at 50 °} C. for 4 hours. The fabric was then in a dispersion of 30.8 g (0.2 mol) of ^ N'-bisacryloyl-methylenediamine, 6.9 g (0.1 mol) of octadecylamine and 7 g of the sodium salt of a coconut fatty alcohol diglycol ether sulfate der'Kettenlängen C ₁₂ ^to C ₁ ^ immersed in 1400 ml Viasser and 70 ml isopropanol at 70 ⁰ C as a dispersant. After pre-drying in air, the mixture was ^{fixed at 120 °} C. for 30 minutes.

After the washing treatment and grip rating as described in Example 1, the following assessment was obtained:

Number of washes - 1 3 6 9 12 15

Handle, 1.4 1.5 1.5 1.8 2.0 2.0

Example 7: ·; - '

Cotton terry fabric was made as in Example 1 with a solution of 48 g of bis (ß-chloropropionyl) ethylenediamine, 32.5 g of behenylamine and 25 g of sodium hydroxide in 2 liters of methanol and fixed. The grip rating showed the following result:

Number of washes 1/3 9

Handle 1.5 1.8 ?, 0

Q0983272052 BATH ORIGMMAL

Claims (14)

1330768 claims: 1.) Process for the permanent finishing of cellulose fibers containing textile materials, characterized in that that the textile material in the presence of alkaline agents with solutions or dispersions of compounds the general formula A) CH ₂ = CH-CO-NH- CH ₃ - NH-CO-CH = CH ₂ , or ClCH ₂ -CH ₂ -CO-NH- I CH ^ where η is an integer from 1 to 6, and B) R ₁ - X - H, wherein R _{1 is} an alkyl radical optionally interrupted by O atoms or -CONH groups with λβ to 36 carbon atoms, X = -NH-, -NR ₂ -, -0- or -S- and Rp denote an alkyl radical with 1 to 2k carbon atoms, optionally interrupted by O atoms and / or substituted by hydroxyl groups, where the radicals R ^ and R ₂ together do not contain more than 36 carbon atoms, where the molar ratio of compounds A): B) is approximately 1.5 - 2.5 ί 1 is / treated, dried and fixed at temperatures above 100 ° C. 2.) Process according to claim 1, characterized in that the molar ratio of the compounds A): B) is 2: 1. 3 ·) Process according to claims 1 and 2, characterized in that the compound A) used is N, N ^l -bisacryloyl-methylenediamine. - 009882/2052 Henkel & Cie GmbH 19. 3 P ^ BB Patent department
D 3720 - 12 ■ - 4.) Method according to claim 1 to 3 »characterized in that that as compound B) a primary or secondary alkylamine, the at least one, optionally through O atoms interrupted alkyl group with 16 to 24 C atoms contains, used. - 5.) The method according to claim 1 to 3 * characterized ,, • that a straight or branched-chain aliphatic alcohol having 16 to 36 carbon atoms ρ is used as compound B). 6.) Method according to claim 1 to 3 *, characterized in that that as compound B) is a partially acylated di- or fatty acid containing a higher 16 to 24 carbon atoms Polyamine with 2 to 6 carbon atoms used. 7.) Method according to claim 1 to 3, characterized in that that an alkyl mercaptan having 16 to 24 carbon atoms is used as compound B). 8.) Method according to claim 1 to 7> characterized in that . that one the compounds A) and B) in a lower ™ aliphatic alcohol with 1 to 4 carbon atoms dissolved used · 9.) Method according to claim 1 to 8, characterized in that that the solvent is mixtures of water and an aliphatic alcohol containing 1 to 4 carbon atoms in Presence of an emulsifier used. 10.) The method according to claim 1 to 9 # characterized in that that sodium hydroxide or potassium hydroxide are used as alkaline agents « 009SS2 / 2052 Henkel & Cie GmbH Patent department. , D 3720 - 13 - " 11.) The method according to claim 1 to 10, characterized in that that the pH of the treatment solutions is above pH 11. 12.) The method according to claim 1 to 11, characterized in that the treatment solutions 5 to 100 g / l of the compounds A) and B) included. 13.) The method according to claim 1 to 12, characterized in that that the fixation at temperatures of 120 ° to 160 ° C performs. 14.) Textile materials containing cellulose fibers, treated
according to claims 1 to 13 Henkel & Cie GmbH in general • · F / (Dr. Haas) (Dr. Benzeil 009882/2052