CS253213B3 - Method of dyeing and/or printing finishing and washing on textile materials containing cellulose fibres - Google Patents

Description

The invention relates to a process for finishing and washing dyeings and / or prints on cellulosic fiber-containing textile materials by means of water-soluble cationic-active polyelectrolytes, according to the author's certificate 245 170.

The invention can be upgraded in textile refinement to increase cellulosic fibers, increase color fastness, and finish dyeing with reactive dyes.

Previously known cellulosic fiber enhancers have been based on the use of quaternary amoonic compounds derived from tertiary amines and epichlorohydrin, with one reactive group - CH2

In ^Hg or -CH ₂

- CH - CH 2.

• 1 ² OH Cl

The increased effects show quaternary ammonium compounds derived from heterocyclic compounds with two nitrogen atoms having two reactive groups. The two reactive groups allow for increased binding to cellulose fibers and at the same time to crosslink cellulose chains.

Stubs (1)

[, - Μ - Y] ^k * to r x ^r - (1) where Y is -CH ₂ - CH - 1 CHo i 2 or - CH - CH - CH ² x / ² OH Cl 0

r is an integer of 1, 2 or 3 k is an integer of 1 or 2

X is an anionic residue of a strong inorganic or organic acid

M is a heterocyclic radical derived from a heterocycle having two nitrogen atoms.

These compounds can also be used to increase the stability of dyeing with substative dyes. Their effect on dyeing with other antonium dyes is only moderate. They also have little effect on dyeing with reactive dyes.

Following dyeing or printing, the dye that is not sufficiently fastened to the fibers has to be removed from the textile material, shocked auxiliary chemicals have to be removed and, in some dye groups, additional dye washability can be additionally reduced, for example.

Washing textile materials in the textile refining process, especially after dyeing and printing, is a lengthy process that places high demands on process water and energy consumption.

Laundry is particularly important and particularly useful in dyeing and printing the cellulosic materials with reactive dyes. When coloring with this group of dyes, it is known that only part of the dye reacts with the cellulose fiber. A very large dye hydrolyzes and must be removed. The stability of the dyeing or printing depends on the degree of Sokoltjolti washing of the hydrolyzed dye.

The solution to the problem of reactive dye washing has been and is directed in the directions.

First of all, reactive systems and dye constitutions are fixed to the fiber with the highest possible yield, so that washing as much as possible less dye is removed.

The second direction, which is also applied in the choice of the dye substitution, is that the hydrolyzed dye is as washable as possible. [0007] Other engineers are involved in the choice of washing procedure, both in terms of technology and in terms of the choice of machinery.

Interesting technologist! is the use of suspensions of surbites. However, their use is hindered by the relatively high cost, and the design of the machinery has been fully solved so that the property can be fully utilized.

Often, a variety of lattice formulations are also used, which are applied at the end of the wash and have the purpose of blocking unwanted dye residues. This procedure is at least of all the above-mentioned moieties since most of the dyes deteriorate the light fastness.

Most of the aforementioned drawbacks are solved by the method of finishing and washing dyeings and / or prints on textile materials, cellulose fibers, water-soluble 13X0X active polyerecrolytes, according to the author's certificate No. 245 170.

The process according to the invention is characterized in that the matt and / or printed matt is matt. reindeer ^ ^p s t r ^pl lt ^Å c ^{h 10 and 100} ° C with an aqueous solution Toer obsařihuí ^0, Ia ^{from 50} g. 1 latiltaktivních polyelectrolytes structural group of formula (2) ^for X ~ _ ^r k + 1 ^{1 x} 11

-CH ₂ -CH-CH ₂ --M --- CH ₂ -CH-CH ₂ - N - (CH ₂ ) _n - N (2)

OH OH L1 where is and is ^is a number number up to 3 which denotes the valency of anion X or 2 to 10 an entire whole anionic residue of a strong inorganic or organic acid an integer of 1 to 4 a bifunctional heterocyclic residue

ΓΝφ

is hydrogen or alkyl having 1 to 4 carbons

The pattern of the cationic polyelectrolyte can also be expressed in complex terms for the repeating chain moieties and substituents in the formula, where: mk + (R) _X J mVr X, r-

r Yippee integer 1 to 3 to Yippee integer 1 or 2 n Yippee integer 2 to 10 X Yippee anionic residue of strong inorganic or organic acids AND Yippee defined as -CH-CH-CH 0 -M ^{to +} -CH 0 -CH-C 2 _O 12 z 2 OH OH

M is a bifunctional defined above as a heterocyclyl radical

- [ ^NR 3 - ^{C 2} 'n] _e - ^NR 4 - ^or for values x = 1

m - ( ^CH 3 J ^[n - ^(CH 2> n ^-NR 3 ⁾ s

-nr ₄ or

- [nr ₃ - (ch ₂ > J _p

- [ _{NR 4} - ^(c H ₂ ) _n for x = 2

R ₁ are -CL, -Oh, or H-BR ₂ is hydrogen, or -A-OH, -A-Cl, -ABH, -ABAR

R, R R are hydrogen or alkyl having a carbon number of 1 to 4 s is an integer of 1 to 4

The cationic polyeleactrolytes are transportable by reacting compounds of formula with multifunctional amines of formula (3) (1) wherein n, s, R 1, R ₄ are as defined above.

The resulting reaction products are at a content of active ingredient of 40 to 60% yellow-brown viscous liquid of specific gravity of 1.3 to 1.5 g.cm < 3 > mixed with water in each ratio.

Some possible uses of the starting materials and their molar ratio in the reaction are shown in Table 1.

Table 2 lists the basic structural units of these compounds.

The compounds of the present invention exhibit a variety of properties applicable in refining technology. In an alkaline environment, they can react with the alcoholic -OH groups of the cellulosic macromolecule and cause crosslinking. By linking groups containing quaternary nitrogen atoms, the dyeing with anionic dyes is greatly enhanced, as is usual with compounds of formula (1).

Against these compounds, the cationic polyelectrolytes have a markedly increased fixing effect on anionic, especially substantive dyes. However, the effect of these substances in the finishing operations after dyeing and printing with reactive dyes is quite surprising and exceptional.

The process according to the invention is characterized by a very intensive washing effect, is usable without any modifications to existing machinery and does not affect the lightfastness of the dyeing and printing. The use of cationic polyelectrolytes represents a significant shortening of the washing process, which saves water, energy and labor costs.

In aqueous solutions of cationic polyelectrolytes, intensive dye desorption and complex formation between the dye and the polyelectrolyte of the invention occur. This complex is not affine and does not adsorb to the cellulose fiber.

In prints and textiles where there is a white or light soil in addition to dark soil, washing of the washed dye into the white soil is thus prevented during washing. The process can be used not only in industrial technology, but also in home washing of textile products with lower washing stability.

The method according to the invention can also be used in the repair of fabrics in which an unfixed reactive dye has been incorporated.

According to the type of machinery, are dosed from 0.1 to 50 gl ^one cationic polyelectrolyte in the aqueous bath and textiles are washed in the bath at 15 to 100 ° C for 10 seconds to 60 minutes. The washing effect increases with the bath temperature, most preferably between 80 and 100 ° C.

The effect of the action of cationic electrolytes containing groups 1 and 2 on substantive dye staining is different from that of reactive dyes. In fact, they act similarly to the known fixing agents derived, for example, from dicyandiamide. Thus, they increase the color fastness. However, unlike known compounds, they do not reduce the light fastness of the dyes.

Due to the appropriate arrangement of the - NH - and - OH groups, the actionactive electrolytes are capable of binding metal cations so that the stable dyeing can be treated with an aqueous salt solution of a suitable metal. This further increases the stability of the wet coloring as well as the color fastness to light.

2+ 2+ 2+ 2+ 2+ 2+ 2+

Suitable water-soluble salts are Ca, Mg, Zn, Cu, Fe, Co, Ni

Aqueous solution for this treatment contains 0.1 to 20 gl ^three divalent or trivalent metal cation. They can be used simultaneously with the cationic polyelectrolyte or subsequently.

The use of the cationic polyelectrolyte finishing and washing process relates to purely cellulosic textile materials and mixtures thereof with synthetic fibers, in particular polyamide, polyester, polyacrylonitrile and triacetate fibers.

The method according to the invention can be used for finishing and washing fabrics in a string or full width, as well as for washing yarns and strands.

The process according to the invention can be carried out on continuous and discontinuous wide-washing machines, without any modification, on scoopers, jugs, jet dyeing machines and dyeing machines.

The method of finishing and washing according to the invention is explained in more detail in the following examples.

He did

Mercerized cotton yarn, dyed at a saturation of 2% by direct orange number С. It 39 was treated at 30 ° C bath containing 1 gI ^3. Compound 1 of Table 1 at a liquor ratio of 1:20 for 10 minutes. It is then centrifuged and dried. The coloring shows very good stability in water, sweat and washing at 40 ° C.

Example 2

Λ

Cotton yarn according to Example 1 was treated in a bath containing 5 gl ^"3. Compound 1 of Table 1 and 2, GL ³ sodium hydroxide at 50 ° C for a liquor ratio of 1:20 for 30 minutes. After washing and neutralizing, the yarn is dried. The dyeing exhibits excellent water, sweat and wash stability at 95 ° C, i.e. a dye with a higher level of fastness than the completion procedure of Example 1.

Example 3

Cotton knitted fabric is pre-treated with the usual coloring and bleaching. Compound No. 2 of Table 1 is treated at a bath ratio of 1:20 with 15 g.l ^-1 sodium hydroxide 6 gl ^3.

Treatment temperature 55 ° C, time 50 minutes.

After washing, the braid is dyed with the conventional reactive blue number С by washing. 4. Against conventional dyeing, the dye has a double use.

Example 4

The 67/33% polyester / cellulose fiber blend is impregnated on the filament with a bath containing

Dispersion blue No.1.73 10 gl ³

Reactive blue No.1.1 3 gl ¹ sodium alginate 2 gl ¹

After drying at 100 ° C and thermosolting at 195 ° C for 50 seconds, the fabric is soaked in a bath containing:

. Compound No. 1 of Table 1 ^hr sodium Hydroxy ^d 60 g.l ^-1 20 g.l1

After passing through the follicle and 70% rinse, the fabric is allowed to rest at room temperature for 10 hours with continuous rotation. During the mating process, the reactive dye is perfectly fixed and the cellulose fiber is crosslinked by the compound of the invention, thereby improving non-inflammatory properties.

Example 5

Cotton fabric printed with six printing inks containing reactive dyes:

AND) Reeactive žluE C. C. AND. 3 (B) Reeactive orange C. C. AND. 5 C) RReactive June C. C. AND. 24 D) RReactive blue C. C. AND. 5 E) RReactive green C. C. AND. 8 F) RReactive black C. C. AND. 8

diatomaceous earth, alkaline and anti-reductive; after steaming fixation, the machine is washed on a 8-compartment machine with the following baths:

1. Cold water 2. water 50 ° C 3. ⁴ · 5. ^{AT i and} MV snaat ^sp olyelektrolyt no. ¹ of taboo ^{plurality of projections 1 2 g "l} \ te ^pl OTA ^la marks ^of 90 ° C 6. water 80 ° C 7. water 50 ° C 8. Cold water

One pass of the fabric through the washing machine at a speed of 70 m / min achieves perfect washing of the non-fixed dye and the print exhibits high water and wash stability. Lightfastness is not affected.

Example 6

Cotton yarn in winding on X-reels is dyed in the usual way on the dyeing machine

Reeactive orange No. c. AND. 4 2.0% Re-active Red No. c. AND. 2 3.5% Re-reactive blue No. c. AND. 4 0.2% After dyeing, the yarn is washed 5 min cold water and another 5 minutes with water temperature of 50 ° C

The yarn is then treated in a water bath containing 2 g.l of cationic polyelectrolyte # 2 of Table 1.

Temperature 90 ° C. time 10 minutes. This is followed by a 50 ° C water wash for 5 minutes and a short rinse with cold water. The durability of this highly saturated water coloring is 4-5 / 4-5 / 4-5, while the coloring completed in the usual manner achieves water resistance values of 4/3/4.

Example 7

Cotton and viscose staple blend is dyed in conventional hydrodynamic dyeing machine

4,5% Reaction red C.I.2

After dyeing, the fabric is washed 5 minutes with water at 20 to 25 ° C, an additional 5 minutes with water at 60 ° C and násleclně from ^p racovává ^p s ⁹⁰ ° ^{C when} the ^b for ¹⁰ minutes in a ^Copper bath containing ^g. l ^C o ¹ cationic ° .yelektrol ^yl no. ³ of the ^{plurality of projections b} with no. 1.

Wet fastness gearbo ^y speakers have complained stability achieved by the conventional procedure completion. '

Example 8

The cotton fabric dyed on the jug with direct mod # CI 78 at 2% saturation was washed with cold water after dyeing and treated at 30 ° C in a bath containing 5 g ^{-1 of} Compound # 1 of Table 1. Bath ratio 1: 5.

Such a stable dyeing exhibits excellent water and wash stability.

Example 9

The cotton fabric dyed and stabilized according to Example 1 is still treated at 60 ° C for 20 minutes in a bath.

2.5 ^g.] ^ ^-1 of an cupric krpstalický ¹ 0 ml.l ^{-1 acetic} acid lečlov ^á

Bath ratio 1: 5

This procedure further increases wash and light fastness.

Table 1 Number Default substances compounds [y. ^m _Y ] ^{k +} ± x ^r - 1 h H - L? - <CH ₂ ) _n - _s - N - R 1 1,3-bis (3-chloro-2-h ^yd rox along ^{yp p} pl) imidazooinium-sslfát 1 mole ethylenediamine 1 mol 2 1,4-bis (3-c: fluoro-2-hliroxyproppl) pyrazinediyl chloride 1 mol diethylenetriamine 0.8 mol 3 1,3-bis (2,3-epoxp ^p ro ^p pl) -imi ^d AZOS l ^ i ^. ^ ^ I IMCL] chloride 1 mole triehethyentetramin 0.6 mol 4 1,3-bis (3-chloro-2-hproxypro ^p pl) with pprimidinediamine sulphonate 1 mol hexameeethylenediamine 1 mol 5 1,4-di (3-chloro-2-hydroxyproppl) - -1-methpiperazinilmacetate 1 mol N, N'-dimethylhexamethylenediamine 1 mol 6 14-di ^{(3-chloro-2-p} hyitoxypro pl) -1,4 (iiethllpiperaoiniumsulfát ethylenediamine 0.8 mol 1 mol

Table 2

Compound number structural unit

ΓβΠ

4 - CH _O - CH - 1 ^{2 CH} ₂ - O ^{2 S} ° ⁴ H 1 H 1 OH --- CH ₂ - CH - CH 1 2 “ ^N - (CH ₂ ) ₆ - N - OH 5 - CH - CH - ² 1 _/ ___ ch ^ coo '- CH _o -NjB N - CH _O - CH ^г / \ -2 ² 1 - CH ₂ - N - 1 (CH ₂ ) ₆ - N - OH CH 3 OH ^OH 3 CHj 6 - CH _O - CH - 1 ^{2 С} ₂ Г - \ / ^С 2 ^Н 5 - ch ₂ - ( : н - ch ₂ - N 1 - CH ₂ - CH ₂ - N - Oh SO ₄ ² (! jh H H

OBJECT OF THE INVENTION

Claims (1)

OBJECT OF THE INVENTION Method of finishing and washing dyeing and / or printing on textile mateeiálech, obsahuuících cellulosic fibers pomooí soluble cationic polyelectrolytes, indicate .mu.Ci in that the dyed and / or printed textile maatriál treated at temperatures of ^10-100 ° C in ^d APPLICABLE ^{extensible ky} on ^the line with the same embrace her ^0, Ia ^{from 50} gl ^ ^ ^-3 vodorozpistný tionakti-vniích ^p ol ^y electrolytes by copyright certificate :! No 245 170 containing a structural group of the general formula (2) -CH-CH ² CHn- ² I ² OH k _v r- r ^v H k + 1 M ^k -CH.-CH-CH -N- ² * 2 OH Г h I (CIL ·) _n -N 2 n - (2) with where r Yippee whole Number 1, 2 or · 3 to Yippee whole number 1 or 2 n Yippee whole number 2 to 10 with Yippee whole number 1, 2, 3 or 4 X is an anionic residue of a strong inorganic or organic acid M is a heterocyclic radical selected from the group consisting of wherein R is hydrogen or alkyl having 1 to 4 carbons.