CS214180B1 - Method of dyeing or printing of textile materials containing cellulose fibres - Google Patents

Description

In ^yn á.lez ^{the ka} th b ^ar outside ^I or ^P ot ^even with ^the alkylated extiln ^{s t s} c ^h m ^ ri-al of ^c e ^{l ch} ulozovy ^fibers and their blends with colyesterovými fibers. When dyeing or printing, high-temperature treatment of the textile material must be carried out.

Dyeing and printing of cellulose fibers using quaternary ammonium compounds of the + Cl “ ^Ch 2 type

- CH - CH ₂ - N - R ₂

^R 3 wherein R 1, R 2 -. ⁰ . . are alkyl

CH ₂

Cl í ¹

- NI ^R 3 r ₂ has recently become a very watched technology and is + Cl “embedded in a row. inventions. The benefits of utilizing these reductions in compound claims are undisputed, in particular, an increase in laundering makes these processes an attractive use of dyes, increased stability and

Further, ^{at the} right of ^alkyl sahuj ^b c ^{d d d} e ^p oxi alkyl group.

^hyd RINOVA with chlorine ^to Stabilize ^No. enyne compound ^Y with a reactive halogen on the carbon chain two-man. Compounds with the latter group react with cellulose only under specific conditions, at temperatures above 180 ° C and in the presence of ammonia releasing agents. It has now been shown that under the same conditions quaternary amines can also react with a reactive halogen on an up to five-membered carbon chain, that is to say the compounds of formula (3):

Wherein X is an anion of a strong inorganic or organic acid,.

Y is a halogen atom, n is a number 3, 4 or 5, ^R 1 f is hydrogen, alkyl or hydroxyalkyl having a carbon number of 1 to 3

R 8 'is alkyl or hydroxyalkyl having a carbon number of 1 to 6, aryl or alkylaryl having a carbon number of up to 12

These novel quaternary ammonium compounds are used in a process for dyeing or printing textile materials containing cellulosic fibers, in particular mixtures of cellulosic and polyester fibers, in which the cellulosic fibers are dyed with anionic dyes using high temperature fixation. ·

Prior to or during dyeing, the textile material is treated with an ammonia cleavage agent during heat treatment at a temperature of 180-230 ° C and a quaternary amine compound of formula (3).

Compounds of this type react with cellulose in the presence of a suture of amorinous release agents at temperatures above 180 ° C to form a bond. In particular, UexampteУenteerapine and ammonium carbonate

This gives the application of these substances to the dyeing and printing of cellulosic materials.

The presence of antioxidants or other excipients such as migration inhibitors and thickeners has been shown not to affect the reaction. As a result, the compounds according to the invention differ significantly from the compounds of the general formulas (1) and (2). ·

The above knowledge can also be used to dye a mixture of cellulosic and polyester fibers with antonic and disperse dyes. At the same time, the dispersion dye on the polyesteo fiber also reacts between the compounds of the invention and cellulose. Kyvatem! the ammonium group simultaneously binds the ionic dye. Since the bath or the printing paste is not alkali, the stability of the dyeing baths or printing pastes is not impaired, and at the same time the use of the dispersion dye in the non-volatile portion is not impaired. To cover the cellulosic moiety, dyes having a reactive, acidic or metal complex complex may be used.

When dyeing or printing, the dyeing baths or printing pastes, in addition to dispersing and aionic dyes, also comprise the compound of formula (3), a heat-treating compound, ammonia and a thickener.

In particular, such compounds are suitable for the dyeing or printing process of the present invention. The compounds of formula (3) having a chlorine or bromine atom of Y and H 2, ^R 2 are methyl groups.

Suitable anions of inorganic acids, for example chloride, bromide, sulphate, phosphate, as well as anions of organic acids, for example aromatic and lower aliphatic sulfoacids, such as benzenesulfonate, p-toluenesulfonate or ethanesulfonate, furthermore anionic acid residues alkyl esters of inorganic acids such as metosulfate or etosiufate.

As representatives of the compounds of formula (3), they may be named as a successor to the compound s

N- (5-ihloramyl) -N, ^ ^τ, N erimetylamoniumcilorid,

N (3-chloropropyl) -N, N, N-trittylammonium bromide,

N (4-bromobblyl) -N, N-dittyl-N-benzylammonium chloride,

N (3-bromonitrile) -N, N-dimethyl-N-ethylammonium sulfide.

These compounds can be prepared by known realities, for example by diluting the thermal amines by dililogeoilCiny according to the scheme.

f \ í ¹

Y-CH ₂ r (CH ₂ ) m -N- H ₂ ^r 3

In _л where the meaning of the symbols Fy, H £, H,, Y, m is the same as that of the general formula (3).

The method of dyeing according to the invention is suitable for trimmings, strands, preferably for fabrics such as fabrics, knitted fabrics or nonwovens. The volatile maize must contain hydroxyl groups such as native cellulose fibers or regenerated cellulose fibers. It may consist of a mixture of these fibers with polyester, polyacrylic or tricetate fibers »

The dyeing and printing process according to the invention is particularly suitable for anionic dyes, which are known by the designation as dyes, bitter, reactive and acidic. These dyes are described in the Color Index, 3rd Edition (1971). Applications of these dyes are given in the examples.

The treatment of the fibers with the compounds of formula (3) is carried out by printing or weaving the textile material with known water baths containing the compounds of formula (3) in an amount of 5-100 g.kg ^-1 , in particular 10-60 g.kg ^-1 . ¹ and an ammonia splitting agent in an amount of 5-100 ^g . ^CG-1, vzta / ENO on famonost t ⁱ ^ f; ^C III paste or kocovácí ^la harvest.

Ammonia cleavers are known compounds used for various industrial purposes.

Compounds suitable for the dyeing and printing process according to the invention are both organic compounds, for example hexameeylenetetramine, and inorganic compounds based on ammonium salts, for example ammonium carbonate.

The printing nasty obsahiu aobvyklé one thickener, for example alaCtomαoaoy ^g, alginates, cards ^ oxy ^ t ^ tylitlulózu, hydroxyeeylcelllOzl, starch or natural gums.

The float bath is applied to the textile material with a degree of unlocking of 60 to 100%. After being hit at a temperature of 70 to 140 ° C, fixation is carried out. The fixation can be carried out by means of dry tenner or steaming with superheated steam. Dry heat and overheated steam fixation. The temperature rises between 180 ° C and 250 ° C for 1 to 15 minutes.

After the fixation is complete, the textile material is stained with a suitable anionic dye. You can do this

using all known discontinuous, semi-continuous or continuous processes suitable for the textile material. . . '

It is advantageous to use the compounds according to the invention such that they comprise part of the impregnating bath or printing paste. an anionic dye, preferably a direct, reactive or acid dye. Under the same technological conditions, the dye is also fixed. The degree of use of the dyes is very high, although full use of the dyes can be achieved with the choice of suitable conditions, particularly. very economically advantageous for reactive dyes. By using substantive agents, a level of stability can be achieved which is in most of the criteria much more expensive reactive, redigozoic and cyanine dyes.

V. The color saturation can be varied on the surface of the compound of formula (3), which can be used to print the pattern containing the compound and then dye with non-color dyes. The effect obtained by printing pastes with different concentrations of the quaternary ammonium compounds of the invention can be further enhanced by the use of selected dyes.

The excellent fixation of the dye in the manner of dyeing and printing according to the invention leads to a shortening of the dyeing time, while the dyeing baths remain almost clean after dyeing. This results in a substantial improvement in the purity of the waste water.

The formation of the ammonium compound of formula (3) can also be used to additionally improve the fastness of dyeing or printing by conventional methods. It is actually a new process for burning anionic dyes. The process is carried out by impregnating the fabric with a water bath containing a quaternary ammonium compound (3) and an ammonia cleavage agent during heat fixation, in particular hexamethylenetriamine and ammonium carbonate. After drying at 70 DEG-140 DEG C., fixation is carried out with superheated steam or hot air at a temperature of 180 DEG to 030 DEG C. for 1 to 15 minutes. The fixed fabric is washed and dried. The fabric treated in this way exhibits a significant improvement in fastness, especially wet and light fastness.

. The quaternary ammonium compounds of formula (3) for dyeing, printing or stabilizing are described in the following examples. Data on the dyes mentioned in the examples are taken from the Celour-Index, 3rd Edition (1971), Volume 4.

Example .1

The pre-treated cotton fabric is tilted on a fullar, at a temperature of 20-25 ° C, with a 80% rinse, with a water bath containing:

gl ^{-1 τ} ^ ( '5-chloro ^l NATM ^{yl) -N, N,} N-tiimeУyaamonium chlorines ²⁰ ёЛ hexamerylentrtram ^{i -1} n

Naklocovaná. the fabric is dried with hot air and a drying hot-tube at 100-110 ° C and fixed in a hot air at 200 ° C for 60 s. The fabric thus treated is stained with dyeing Direct Blue C.I. 107, with a saturation of 2% of the woven fabric. The jig is stained without any other ingredients. The dye is dosed into the jug at 30 ° C, after which two seedings of 30 ° C, two passages at 60 ° C and four passages at 90 ° C are dyed. with very good stability, especially in wet and light conditions. The use of dye on the jug is very high so that the dye is drained from the Dractically bath.

A similar result is obtained when another direct dye, for example, is used in the dye bath on the jug

Direct yellow C.I. 26,

Direct yellow C.I. 29,

Straight orange C.I. 39,

Straight Red C.I. 80,

Straight Red C.I. 76,

Direct Violet C.I. 48,

Direct Violet C.I. 46,

Straight Blue C.I. 106,

Straight Blue C.I. 71,

Spot Blue C.I, 78,

Straight Blue C.I. 86,

Direct green C.I. 28,

Direct anger C.I. 103,

Straight Brown C.I. 218,

Straight Black C.I. 56,

Other compounds have a similar effect to the quaternary ammonium compound used, for example:

N (4-bromobutyl) -N, N-diethyl-N-benzylammonium chloride,

N (3-bromopropyl) -N, N-dimethyl-N-ethylammonium sulfate.

A similar effect is obtained when ammonium carbonate is used instead of hexamethylenetetramine.

PříkjaJ 2

The pretreated fabric of a mixture of 67% cotton and 33% viscose staple is printed with a printing paste containing g of N (N-chloropropyl) -N, N, N-trimethylammonium bromide, g of Reactive Red C.I. 2 g of hexamethylenetetramine, g of sodium alginate, 4% aqueous solution,

875 g of water

000 g

The printing and drying is carried out by the stencil printing technique known in the art. The dried fabric is hot-air fixed at 205 ° C for 60 s. The usual washing and soaping follows. The resulting printing exhibits extremely good stability, especially in wet conditions and high dye utilization. A similar result is obtained when another reactive dye, e.g.

Reactive Yellow C.I. 3,

Reactive yellow C.I. 2,

Reactive Orange C.I. 12,

Reactive Orange C.I. .5,.

Reactive Orange C.I. ' 13,

Reactive Red C.I. 24,

Reactive Red C.I. 45,

Reactive ^and worm ^least 'CI 31

Reactive Violet C.I, 1,

Reactive Blue C.I. 5 ,.

Reactive Blue C.I. 13,.

Reactive Green C.I. 8,

Reactive‘ brown C.I. 2,

Reactive Black C.I. 8,

The following compounds have a similar effect to the quaternary ammonium compound used:

N (3-chloropropyl) -N, N, N-trimethylammonium bromide

N (3-bromopropyl) -N, N-dimethyl-N-ethylammonium sulfate.

A similar effect is obtained when ammonium carbonate is used instead of hexamethylenetetramine.

Example 3 '

Fabric of viscose staple, dyed. Direct orange C.I. 39, is tilted at ambient temperature with a water bath containing:

gl ¹ N- ^{(4-Bromo b} ut ^yl) -N, ^{Nd, and} E ^b N ^tulle enzylamonium Florid

gl ^{1 1} u ^h l ^h an ammonium

An Naklocovaná ^{tk on} the usu ^{Si fi} fixes the autoclaved p ^s at ^{190 Q} C ^d a ^b for ⁹⁰ s. ^P o fixation se.tkanina washed with a regular procedure for širokopracím machine and hot stuednou water and again dried.

This process is very suitable for improving the fastness to dyeing which has been carried out by the known process for direct dyes.

A similar effect is obtained when the following quaternary ammonium compounds are used: N (2-bromoethyl) -N-hydroxyethyl-N, N-dimethylammonium metosulfate,

N (2-chloroethyl) -N, N, N-trimethylammonium bromide,

N (3-chloropropyl) -N, N, N-trimethylammonium bromide,

N (3-bromopropyl) -N, N-dimethyl-N-ethylammonium sulfate, N (2-chloroethyl) -N, N, N-trimethylammonium metosulfate, N (p-bromoethyl) -N, N-dimethyl-N-hydroxyethylammonium acetate.

A similar result is obtained when hexamethylenephthramine is used instead of ammonium carbonate.

Claims (2)

Method for dyeing or printing textile materials containing cellulosic fibers, in particular mixtures of cellulosic and polyester fibers, in which the cellulosic fibers are dyed with anionic dyes using high-temperature fixation, characterized in that the textile matteial is treated with a substance before or after dyeing , leaving off ammonia during heat treatment at a temperature of 180 to 230 ° C and a quaternary ammonium compound of formula r ₂ wherein X is an anion of a strong inorganic or organic acid, Y is a halogen atom, n is a number 3, 4 or 5, R 3 ^R j ^is hydrogen, alkyl or hydroxyalkyl having a carbon number of 1 to 3 R 1 is alkyl or hydroxyalkyl having a carbon number of 1/6, aryl or alkylaryl having a carbon number of 6-12. 2. A method of dyeing and / or printing as claimed in claim 1, wherein the ammonia-separating substance is treated with hexamethyleatetain or ammonium carbonate.