CH646448A5 - TRISAZO CONNECTIONS. - Google Patents

Description

The present invention relates to trisazo compounds in the form of the free acid of the formula:

55

X-HN? H "j00! OCH} ÇH

OJO

H05S nS0jH

N = N- / Ö) - (Ö) —N = N -r ^ Yq]

"• NHR

(1)

N = N- ^ Ô ^ NO;

COOH

60

(1)

65

correspond in which R is hydrogen, methyl or phenyl and X is acetyl, benzenesulfonyl, toluenesulfonyl, chlorobenzenesulfonyl or a group of the formula:

n = N- ^ O ^ —NO 2

COOH

was disclosed in Example 11 of Japanese Patent Publication No. 1893/1956 as a dye having a hue similar to that given above. This dye is well suited for high temperature dyeing in an acidic bath (i.e. the ability to dye cellulosic fibers under the dyeing conditions used for dyeing polyester fibers with disperse dyes). However, this dye, on the other hand, has poor washing fastness and poor chlorine fastness (there are dyes that are severely discolored or faded even by a very small amount of active chlorine contained in the tap water used for water in cities. This fact is particularly evident in recently a problem in this area). As a result, there has been a strong desire to develop navy blue direct dyes that are well suited for high temperature dyeing in an acidic bath and fastness to washing, chlorine, etc.

The aim of the present invention is to provide new trisazo compounds which meet the above requirements and are well suited for high-temperature dyeing in an acidic bath and which contain polyester-cellulose mixtures.

3rd

646 448

fibers together with a disperse dye can dye with excellent fastness properties using the one-bath single-stage dyeing process to produce navy blue dyeing.

The new trisazo compounds according to the invention can be produced by the following process:

One mole of tetrazotized 4,4'-diamino-3,3'-dimethoxydiphenyl is at a temperature of up to 20 ° C, preferably 0 to 5 ° C, under neutral or alkaline conditions with one mole of a coupling component, which is in the form of the free Acidity of the formula:

X-HN OH

HO jS 'SO j H

corresponds, coupled. Then the product thus obtained is further mixed with one mole of a compound which is in the form of the free acid of the formula:

OH

(2)

[OTO

NHR

H ° jS N = N- / 5VN02

(3)

COOH

corresponds, coupled, preferably in the presence of a coupling accelerator, such as pyridine, under alkaline conditions to form the trisazo compound.

Another process for the preparation of the trisazo compounds according to the invention is to couple a mole of tetrazotized 4,4'-diamino-3,3'-dimethoxydiphenyl with one mole of a compound of the above formula 3 under neutral or alkaline conditions and then to further couple this product with one To couple moles of a coupling component of formula 2 above, preferably in the presence of a coupling accelerator, such as pyridine, under alkaline conditions.

As coupling component of formula 2 above, e.g. to be named:

l-acetylamino-8-naphthol-3,6-disulfonic acid, l-benzenesulfonylamino-8-naphthol-3,6-disulfonic acid, l- (4'-methylbenzenesulfonylamino) -8-naphthol-3,6-disulfonic acid,

1- (4'-Chlorobenzenesulfonylamino) -8-naphthol-3,6-disulfonic acid and compounds of the formula:

^) - NH-C * '^ C-HN OH

| SOjH SOî H W

(4)

where W is an alkanolamine residue, such as a monoethanolamine or diethanolamine residue, a glycine residue, a sarcosine residue, a taurine residue, an N- (β-hydroxyethyl) methylamine residue or a morpholine residue which is bonded to the triazine nucleus via its nitrogen atom.

The following can be mentioned as compounds of the above formula 3:

Oll

(OlPj-NU 3

ho, s

N = N- ^ 0) - NOj 110> S N = N - ^) - N03 "° 5S H = N- (O) -NOi

COOII

COOH

The new trisazo compounds according to the invention are capable of natural or artificial cellulose fibers in navy blue shades with a very high dyeing value and excellent waterfastness, washfastness. Lightfastness, light / sweat

to dye or print fastness and fastness to chlorine by means of various dyeing or printing processes which are carried out under the usual conditions for dyeing or printing cellulose fibers with direct dyes, such as dip dyeing, continuous dyeing or printing with a color paste, by means of dyeing or printing processes which are carried out under the conditions normally used for dyeing or printing polyester fibers with disperse dyes, such as high-temperature dyeing, io carrier dyeing, thermosol dyeing or printing,

or by means of dyeing or printing methods which are carried out under the conditions normally used for dyeing or printing acrylic fibers with cationic dyes, such as dip dyeing in an aqueous medium or printing with a color paste which contains a dyeing aid.

Of the trisazo compounds according to the invention, those of the above formula 1 in which X is tosyl and R is hydrogen or phenyl are particularly preferred.

One can proceed in such a way that a dyeing liquor or printing paste which contains the trisazo compound according to the invention alone or a mixture of the trisazo compound according to the invention with other dyes, such as disperse dyes or cationic dyes, and cellulose fibers, polyester-cellulose mixed fibers or mixed textiles or polyacrylic-25 cellulose mixed fibers or mixed textiles with the dye liquor or printing paste thus produced, dyed or printed according to any dyeing or printing process. Then one can subject the dyed or printed fibers to copper treatment, i.e. H. preferably a fixing treatment by putting the above fibers in an aqueous solution of a copper-containing fixing agent of the polyamine type, for example, to form a copper-containing complex salt on the fibers at 15 to 80 ° C, whereby the dyeing is completed.

The trisazo compounds according to the invention have the advantage that when dyeing polyester-cellulose mixed fibers with a trisazo compound according to the invention and a disperse dye according to the single-bath dyeing process under the dyeing conditions for disperse dyes, the cellulose fraction of the mixed fibers can be dyed uniformly. The dispersion dyes that can be used in combination with the trisazo compounds according to the invention include, for. B. C.I. Disperse Blue 39, C.I. Disperse Blue 49, C.I. Disperse Blue 75, C.I. Disperse Blue 79, C.I. Disperse Blue 125, C.I. Disperse Blue 270, C.I. Disperse Blue 259 and C.I. Disperse 45 Blue 283.

The present invention will now be described in more detail with the aid of the following examples, which, however, is in no way intended to limit the scope of the invention. In the following examples, parts are parts by weight, unless stated otherwise, and all starting compounds and products with water-soluble groups are shown in the form of the free acid.

55 Example 1

4.88 parts of dianisidine were added to 40 parts of water and 10.9 parts of hydrochloric acid, and ice was further added to the mixture. Then the tetrazotization was carried out at 13 to 15 ° C for two hours using 2.9 parts of sodium nitrite 60.

An alkaline solution was added to the above reaction mixture by dissolving 9.9 parts of l- (4'-methyl-benzenesulfonylamino-8-naphthol-3,6-disulfonic acid, 12 parts of anhydrous soda and 2.7 parts of 47% sodium hydroxide was prepared in 65 100 parts of water The reaction was carried out at 0 to 5 ° C., the pH being kept at 10.5 to 11, until tetrazotized dianisidine could no longer be detected by a spot test.

646 448

4th

8.7 parts of a compound of the formula:

OH

JSISXnhz H ° 3S H = N- ^ 0) -no2

COOH

OCH3 OH

C5)

and 4.3 parts of a 47% sodium hydroxide solution were dissolved in 100 parts of water and 100 parts of pyridine, and the resulting solution was added to the above solution of the primary coupling product, and the mixture was stirred overnight.

The next morning, the pyridine was recovered by steam distillation and 24 parts of a 35% hydrochloric acid solution were added to the liquid reaction mixture, followed by the addition of sodium chloride in an amount of 10% based on the liquid to effect salting out, followed by the product filtered off and dried.

The compound of the formula obtained:

N = N— (O _

NH2 (6)

-y |

5 —CO) —NO z was soluble in water to form a blue solution. The value of Imax was 620 nm.

Examples 2 to 17 The same procedure as in Example 1 was repeated except that the compound AH from the following table instead of 1- (4'-methylbenzenesulfonylla-mino) -8-naphthol-3,6-disulfonic acid and the compound BH from the following table were used instead of the compound of formula 5 above, wherein a compound of formula:

15 and 3 OCF. ~

A-N = N - ^ - @ - n = N-B

wherein the azo group is bonded to an hydroxyl group in the naphthalene nucleus of A or B, 20 was obtained.

Example No.

AFI formula

Formula bra

^ • max ^ -n aq. ^ .Er

Solution-

2nd

'CH3COHN OH

HO 3S SO3H

OH

(9®-NH2 H ° 3S N = N - ^) - N0 2 COOH

600

3rd

do.

OH

NHCH3

H0> S

COOH

605

4th

do.

OH

. jè®-NHr @

H ° 3S N = N - (^) - NÖ2

COOH

597

5

@ ~ SO2HN OH

forò

HO3S S03H

OH

ho3s n = n- (o) -no2

COOH

617

6

do.

OH

(è © ~ NHCH3 H ° 3S N = N-i ^) - N02

COOH

620

5

646 448

Example No.

Formula All

Formula bra

^ max. ^ -n VJässri [; er

Solution_

7

ci - @ - so2hn oh ho3s sq3h

OH

JO ^ InHz

H ° 3 • N = N - ^ - NOz COOH

618

8th

CH3 - @ - S02HN OH

fètè}

ho3s so3h

OH

fo £ o) _NHCH 3 Ö ° 3S N = N - ^) - N02

COOH

625

10th

do.

(^ ®-NH- (o}

h ° 3S U- ^ no2

COOH

615

11

(0> HN-C C-HN OH

VÄ

HOH2CH2CHN S03H h03S

OH

/ è® "NH

HO3S

COOH

605

12

, N ^

(oV-HN-C C -HN OH

«1 1A

v Ä

H0H2CH2CJT S0_H H0-, S HOH2CH2C 3 3

do.

605

13

(OhHN-C C-HN OH

v Ä

^ ch2-H, CJ SO, H HOxS

° -CH! -CÄa'N 3 3

do.

605

14

rs

(o) -HN-C C-HN

II I / PH

HOOCH, cJ. ®3S

OH

/ Ô®-NH2 hd3S N = N- ^ NOj

COOH

605

646 448

6

Example No.

Formula All

Formula bra

^ • max in v.'ässrij; he

Solution-

15

@> - HN - <* NC— HN OH

\ SCUH H0, S H03SH2CH2CHN 5 3

do.

605

16

/ - \ A

(OV-HN-C C-HN OH

v Ä

HOOCH 2 C- ^ S03H H03S

ch3

OH

/ ^ © -NHCH ^

H03S N = N- <p) - N02

COOH

610

17th

(OVHN-C C-HN OH

y Ä

| SO H H0, S

ho3sh2ch2chn 3

OH

/ éiY) -NH- ©

SO3H N = N - ^} no2 COOH

603

Example 18

High-temperature single-bath dyeing of polyester-cotton mixed fibers

A dye liquor of pH 4.5 was made from 0.4 part of the compound of the above formula 6.10 parts of anhydrous sodium sulfate, 0.8 part of Kayaion Polyester Navy Blue BX-SF Paste 100 (a disperse dye from the patentee), 0.64 parts Sodium acetate trihydrate, 0.42 parts acetic acid and 400 parts water. The temperature of the dye liquor was controlled at 50 ° C and 20 parts of polyester-cotton mixed fibers (50/50) were immersed in the liquor. The temperature was raised to 130 ° C over 30 minutes, and the dyeing operation was carried out at this elevated temperature for 45 minutes. Then the temperature was lowered to 90 ° C over a period of 15 minutes, and the dyeing operation was continued at this temperature for 15 minutes.

The dyed fibers were removed from the dye liquor, washed with water, at 60 ° C for 20 minutes, with a fixing treatment with an aqueous solution, which was carried out by dissolving 1.2 parts of a commercially available copper-polyamine fixing agent (San Fix 555C , a product of San'yo Kasei Co., Ltd.) in 400 parts of water, subjected to, soaped, washed with water and dried.

35

The dyed polyester-cotton mixed fibers obtained had a level navy blue color with excellent fastness to light, washing and chlorine.

Example 19 Dyeing Acrylic-Cotton Mixed Fibers 40 A dye liquor of pH 4.5 was made from 1 part of the compound of the above formula 6.16 parts of anhydrous sodium sulfate, 0.4 part of Kayacryl Navy Blue BL (a cationic dye of the patent owner), 1. 51 parts of sodium acetate trihydrate, 0.89 parts of acetic acid, 2.4 parts of Sun Salt LS (a flocculation 45 inhibitor from Nikka Kagaku Co.) and 1178 parts of water.

The temperature of the dye liquor was adjusted to 50 ° C and 40 parts of acrylic-cotton mixed fibers (50:50) were immersed in it. The temperature was raised to 50-100 ° C over 20 minutes, and the dyeing operation was carried out at this elevated temperature for 30 minutes.

After dyeing, the dyed fibers were taken out, washed with water, fixed with a commercially available copper-polyamide fixing agent in the same manner as in Example 55, washed with water and dried.

The dyed acrylic-cotton mixed fibers had a level navy blue color with excellent light, wash and chlorine fastness.

60

Claims (3)

646 448 2nd PATENT CLAIMS 1. Trisazo compound, which in the form of the free acid of the formula: l II W v / 1 X-HN? H H3C0 \ OCH, H0- o o N = NHfoWÖ} —N = N -YQT6) -NHR SOYH (1) 10th N = N- ^ 0 ^ NO 2 COOH where R is hydrogen, methyl or phenyl and X is acetyl, benzenesulfonyl, toluenesulfonyl, chlorobenzene-15 sulfonyl or a group of the formula: rv <ö> vn 20th means, where W is an aliphatic amine radical having up to 4 carbon atoms which is substituted by hydroxyl, carboxyl or sulfo, or a morpholine radical which is bonded to the triazine nucleus via a nitrogen atom. 2. Trisazo compound according to claim 1, characterized in that it is in the form of the free acid of the formula: KJC - ^^ - SO2HN 9h HjCn OCHJ 25th 30th HOjS sS03H HO ,; NHj K = N- / ÖV-N02 35 corresponds. 3. Trisazo compound according to claim 1, characterized in that it is in the form of the free acid of the formula: means, where W is an aliphatic amine radical having up to 4 carbon atoms which is substituted by hydroxyl, carboxyl or sulfo, or a morpholine radical which is bonded to the triazine nucleus via its nitrogen atom. Many direct dyes which are able to dye or print cellulose fibers in navy blue shades with good light and wash fastness have already been disclosed in various patents and literature references; Dyes of this type, e.g. B. C.I. Direct Blue 248, 150 and 157 were used on a commercial basis. It is currently particularly preferred when dyeing or printing polyester-cellulose loose fibers to dye or print the polyester portion with a disperse dye and the cellulose portion with a direct dye at the same time, namely under the dyeing or. Printing conditions for the disperse dye in order to reduce the dyeing or printing time and to save labor and energy, since the dyeing or printing costs in dyeing and printing plants have increased as a result of the rise in labor costs and the oil price. However, when polyester-cellulose mixed fibers are dyed with the above direct dyes together with disperse dyes at high temperatures according to the one-bath immersion dyeing method, the following disadvantages are inevitable: (1) The dye adsorption is drastically reduced. (2) Dye coagulation occurs in the dye liquor. (3) The viscosity of the dye liquor is increased and no level dyeing is available. Therefore, a two-bath two-stage dyeing process or a one-bath two-stage dyeing process (where the polyester portion is first colored with the disperse dye and the cellulose portion is then colored with the direct dye) must be used, which is not preferable in view of saving labor and energy becomes. A dye of the structure: 40 ij N = N corresponds. 50