CH660195A5 - DISAZO CONNECTIONS. - Google Patents

Description

The present invention relates to disazo compounds which, in the form of the free acid, correspond to the formula (1):

x- ^ nvt f11 qh

Would

'Vx'

ior (i)

in which X and X 'independently of one another correspond to one of the groups represented by the following formulas (2) and (3):

__ ^ - COOH

• NH- / 0V0H

^ COOH

—Nh - (o) - oh so3h

(2)

(3)

Y and Y 'each independently represent a group of formula (5a)

Ri

(5ä),

«3

in which Ri is hydrogen or a methyl or ethyl group and R2 and R3 each independently of one another water-60 substance or chlorine atoms, or a methyl, methoxy,

Hydroxyl or carboxyl group or groups of the formulas -NHC2H4OH or -N (C2H40H) 2, or a copper complex salt thereof and a mixture which contains the disazo compound and copper complex salts thereof ("Kup-65 ferkomplexsalzen" contain a compound which contains a copper atom contains in a molecule of the bond and a compound which has two copper atoms in one molecule of the compound: these forms are used here); the inven

660 195

4th

also relates to dyeing processes for cellulosic fibers, i.e. generally fibers based on natural, regenerated or chemically modified cellulose.

In line with the increasing demands of the market, there are increasing demands on the authenticity of dyed goods, in particular textile goods. In accordance with these requirements, reactive dyes are often used to dye cellulosic fibers. When dyeing cellulosic fibers with reactive dyes, however, large amounts of inorganic salts such as Glauber's salt and alkali such as sodium carbonate are required, and methods for removing unfixed dye after dyeing are also required. Such a procedure is therefore disadvantageous from the point of view of energy consumption for dyeing cellulosic fiber material. Furthermore, reactive dyes have the serious disadvantage that mixed fabrics made of polyester and cellulose cannot be dyed simultaneously with the reactive dye and a disperse dye in a weakly acid bath at high temperatures. On the other hand, only a very simple dyeing method is required for dyeing with a direct dye, and dyeing can be carried out in a short time and in the presence of small amounts of a neutral salt such as Glauber's salt without the need for post-treatments. The direct dyes are therefore superior to the reactive dyes in terms of the simplicity of the dyeing process and the economy in the use of raw materials and energy.

The conventional blue direct dyes are only used for dyeing cotton fibers in weak or pale tints, since good dye fastness cannot be achieved with these dyes if the cotton fibers are dyed in medium or deep tints. Furthermore, there are very few direct dyes with good chlorine fastness. For these reasons, the development of blue direct dyes with excellent wash fastness and chlorine resistance was an important task.

5 After extensive investigations with the aim of developing blue direct dyes of excellent fastness, both for washing and for chlorine, it was found that it is possible to use the disazo compound of the formula (1) given above, the copper complex salts io previously or the mixtures of such disazo compounds and their copper complex salts , a bright blue color with excellent fastness is available not only against chlorine, but also against washing. The compound according to the invention and the mixtures according to the invention can be used for dyeing not only cellulosic fibers, such as rayon, cotton and hemp, but also mixed fibers, such as polyester / rayon blended fabrics, polyester / cotton blended fabrics, polyacrylic / cotton Blended fabrics, polyamide / cotton blended fabrics and wool / tree-20 wool blended fabrics can be used by one-bath, one-step dyeing processes and in the presence of other types of dyes.

The disazo compound of the formula (1), a copper complex salt thereof and the mixture containing the compound of the formula (1) and its copper complex salts are generally prepared by the following processes:

Dianisidine- (4,4'-diamino-3,3'-dimethoxydiphenyl) is tetrazotized and the tetrazonium compound is coupled with 1-amino-8-naphthol-3,6-disulfonic acid to obtain a disazo-30 compound, which is in the form of the free compound Acid has the following formula (4), to which reference is made below:

tinJN un rtar so3h s ° 3h och

(4)

so3h

Then the disazo compound of the formula (4) is condensed with a cyanuric trihalide, such as cyanuric bromide, cyanuric fluoride or preferably cyanuric chloride (first condensation), and the product obtained with 3-carboxy-4-hydroxy-aniline or 3-sulfo-4-hydroxy-5 -carboxyaniline (second condensation) condensed. The product is then further treated with a compound of the formula (5)

nh I

R1

(5)

condenses in which Ri is hydrogen, methyl or ethyl and R2 and Rs each independently, hydrogen or chlorine or a methyl, methoxy, hydroxyl or carbo-

45 xyl group, monoethanolamine or diethanolamine mean (third condensation) to obtain a disazo compound of the formula (1).

The mixture of a compound of formula (1) and copper complex salts thereof is prepared as follows: 50 An accelerator for copper complexation such as monoethanolamine, diethanolamine, N-methylethanolamine or ammonia is added to the reaction liquid, if necessary, which contains the compound obtained according to the above information of formula (4) contains. Then, a copper complexing agent such as copper sulfate, copper acetate or copper chloride is reacted to cause a partial copper complexation reaction. This gives a mixture of the compounds of the formulas (4), (6) and (7):

60

, h2n p Cu — 0 PCH 3 ho nh2

■ n2—— n2 — to ^ ol so3h so, h

(6)

660 195

h2n 0

so3h

(7)

Regarding the proportions of each of the compounds of the formulas (4), (6) and (7) in the mixture, the liquid for the copper complexation reaction is examined by liquid chromatography analysis and the amount of the copper complexing agent, the reaction temperature and the reaction time are controlled so that Proportions of 20-60% of compound (4), 40-60% of compound (6) and up to 20% of compound (7) arise, the percentage values corresponding to the area ratios of the liquid chromatography diagram.

The preferred conditions for the partial copper complexation of the compound of formula (4) are as follows:

The proportion of copper complexing agent is 0.7 to 1.5 mol per 1 mol of the compound of formula (4), the reaction temperature is 80-100 ° C and the reaction time 5-20 hours.

If necessary, the compound of formula (4) can be filtered before the copper complexation reaction and dissolved in water.

The total copper complexation of the compound of formula (4) is carried out by increasing the proportion of copper complexing agent, increasing the reaction temperature 15 and choosing the reaction time longer than that for the preparation of the mixture of compounds of the formulas (4), (6) and (7) corresponds to the specified values and, if necessary, uses an accelerator for copper complexation, such as mono- or diethanolamine, N-methylethanolamine or 2o ammonia.

The first, second and third condensations are effected using the mixture of compounds of formulas (4), (6) and (7) to obtain a mixture of compounds of formulas (1), (8) and (9):

SO-yH

(1)

o-Çv- ^ N

"■ -ro®, Y

soìh s03h

(8th)

(9)

in which X, X ', Y, Y' have the meaning given above. The proportions of these compounds are 20-60% (1), 40-60% (8) and up to 20% (9). Particularly excellent results according to the present invention can be obtained if the proportions are set to 30-45% (1), 40-50% (8) and up to 10% (9).

Compounds of formula (5) include aniline and aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, o-toluidine, m-toluidine, p-toluidine, p-anisidine, 2,5-xylidine, p -Cresidine, m-chloroaniline, p-amino salicylic acid, m-aminophenol, p-aminophenol, p-aminobenzoic acid and 2-chloro-4-methylaniline.

The condensation from the first to the third condensation can be effected by conventional methods. The following explanation gives preferred reaction conditions: the first condensation is carried out at 0-30 ° C. and a pH of 2-7, preferably at 5-15 ° C. and a pH of 4 to 6.5; the second condensation is carried out at 20-70 ° C and a pH of 4-7, preferably at 40-60 ° C and a pH of 5-7; the

60

third condensation is carried out at 80-100 ° C and a pH of 2-10, preferably at 85-95 ° C and a pH of 2 to 4.5 (in the case of aniline and aniline derivatives) or a pH -Value from 9-10 (in the case of mono- or diethanolamine).

The compound of formula (1) or mixture of compounds of formulas (1), (8) and (9) obtained in this way can be separated off by customary methods. In particular, it can be salted out in a conventional manner, filtered and dried if necessary.

The compound (1), a copper complex salt thereof and the mixture of the compounds of the formulas (1), (8) and (9) according to the present invention are characterized in that when used for dyeing cellulosic fibers, in particular cotton fibers and Fabrics containing cotton, blue dyeings with excellent wet and chlorine fastness result. It should also be noted

that they have excellent resistance to high temperatures under acidic conditions and are accordingly suitable for dyeing blended fabrics made of syn

660195

6

thesis fibers and cotton, in particular polyester / cotton blended fabrics, in uniform shades in the presence of a disperse dye for polyester fibers under the dyeing conditions of polyester fibers.

The following examples illustrate the invention. Parts are by weight and the car-boxyl and sulfonic acid groups are shown in the form of the free acids.

example 1

3.7 parts of dianisidine (4,4'-diamino-3,3'-dimethoxydiphenyl) were suspended in 25 parts of water containing 0.1 part of "Liponox NA" (brand name for a nonionic surfactant). 7.8 parts of hydrochloric acid were added to the suspension. The mixture was cooled to 5-8 ° C with ice. 2.2 parts of sodium nitrite (in an approximately 40% aqueous solution) were added over a period of 30 minutes to effect a tetrazotization reaction at 15-20 ° C. for 3 hours. Then the nitrous acid was mixed with sulfamic acid. The tetrazotization reaction liquid became a solution of 10.2 parts of H acid

(l-Amino-8-naphthol-3,6-disulfonic acid) in 60 parts of water and 15 parts of sodium carbonate are added slowly over a period of 20 minutes at 8-12 ° C. After stirring for 5 hours, the reaction liquid was heated to 88-90 ° C. 3.2 parts of mono-5 ethanolamine, 11 parts of ammonia (28% aqueous solution) and 4.5 parts of copper sulfate were subsequently added to the reaction liquid and the mixture was heated to 88-90 ° C. for about 7 hours in order to complex the copper parts to effect. The copper complexation reaction was terminated when the ratio of the compounds of the formulas (4) to (6) (assessed on the basis of the corresponding area ratios in the liquid chromatography diagram) had reached a value of approximately 1.

After completion of the copper complexation reaction, 5 about 50 parts of sodium chloride were added to salt out. After filtering, a mixture of compounds of the formulas (4), (6) and (7) was obtained. The proportions of these compounds were 42% (4), 50% (6) and 8% (7) (assessed on the basis of the area ratios in the liquid chromatographic diagram).

OH NH2

NH2 OH ° fH3 pch 3 OH NH2

S03H S03H SO3H Si

; OoH so-,

(4)

OCH.

OH NH-

(6)

O — 'Cu rSor ^ - ^ Hò ^ "'

SW ^ S ° 3H

3rd

(7)

10 parts of the disazo compound mixture was dispersed in 100 parts of warm water containing 0.1 part of "Liponox NA". About 1 part of hydrochloric acid was added to the dispersion to adjust the pH to 7-8. An appropriate amount of ice was added to keep the temperature at 8-10 ° C. Then 3.8 parts of cyanuric chloride were added and the mixture was stirred at 8-12 ° C. for 3 hours to complete the reaction, the pH of the reaction liquid being kept between 6.0 and 6.5 (first condensation). A solution of 3.1 parts of 5-aminosalicylic acid in 20 parts of warm water and 1.6 parts of a 48% aqueous sodium hydroxide solution was added to the reaction liquid. The temperature was raised to 58-60 ° C. In the course of the temperature increase, the pH of the

45 reaction liquid kept at 6.0 to 6.5 by adding 10% aqueous sodium carbonate solution. The reaction was carried out at these pH and temperature values for 3 hours (second condensation). Then 4.3 parts of m-tolui-din were added to the reaction mixture and the pH of the mixture in this way was adjusted to 5.0 to 5.5 with 5 parts of hydrochloric acid. The temperature was raised to 93-95 ° C and the reaction was run at this temperature for 4 hours (third condensation). After completion of the reaction, 3.5 parts of soda were added to adjust the pH to 8.5 to 9.0 55. 15 g / cm 3 of sodium chloride, based on the liquid, were added for salting out. The resulting crystalline material was filtered off and dried to obtain a mixture of the following compounds:

COOH

OCH-:

OCH 3

COOH

7

660 195

cooh

Le s03h cooh

NH -Zj; ..

oh oh n

cooh

-Cu-

cooh oh

When this mixture was dissolved in water, a solution with an A, max of 607 nm (in 20% aqueous pyridine solution) was obtained.

Example 2

Following the procedure outlined in Example 1, the disazo compound mixture was reacted with cyanuric chloride to effect the first condensation.

Then, a solution of 4.7 parts of 5-amino-3-sulfo-salicylic acid in 20 parts of warm water, which was obtained using 1.6 parts of a 48% aqueous sodium hydroxide solution, was added to the reaction mixture. The temperature of the reaction mixture was raised to 58-60 ° C. In the course of the temperature rise, the pH of the reaction mixture was kept at 6.0 to 6.5 by adding 10% aqueous sodium carbonate solution. The reaction was run at these pH and temperature values for 3 hours (second condensation). The third condensation was carried out with m-toluidine in the same manner as in Example 1. After salting out and subsequent filtering and drying, a mixture of disazo compounds of the following formulas was obtained:

cooh ho-toynh ^ n

/ —7 n >> N I O

so, h i hn so3h cooh nh oh

och

so3h

HO-ZO ^ -Nttf ^ -, NH 0- "T

cu-o

/ - R

s03h nh so-.h so-.h ch.

cooh och 3 0h jjh r'îî

O I O

N ^ N nh cooh 0) —oh so3H

so3h ho3s ch.

o n

cooh

3 oh nh — f vhnnovoh nyn ^

nh ch.

so3H

1

I NC-N

S03H SO ^ IO

ch-

When this mixture was dissolved in water, a blue solution with an Xmax of 606 nm (in a 20% aqueous pyridine solution) was obtained. When using this

Dye for dyeing cellulose fibers was obtained a blue color with excellent resistance to chlorine and washing conditions.

660195

8th

Example 3 Sodium chloride in an amount of 15 g / cm 3 for salting out

A disazo compound added by coupling Dianisi-. After filtering off, a disazoverbin with H acid was obtained in the same manner as in Example 1, using the following formula:

Liisazuveromuung, uie uuiun ivuppcni from uiamsi din with H-acid in the same manner as in Example 1, was heated to 80-90 ° C. Then nh2 oh och.

och

oh nh

so3H

\ 3/3 tt2

o [o

(4)

s03h

S03H

s03h

9.5 parts of the disazozes obtained according to the above information and subsequent filtering and drying were obtained. The compound of the first formula described in Example 1 was obtained with the following formula:

subjected to second and third condensation. According to

a cooh ho- / oVnh-t'n v-

nh cooh

° ^ 3? Ch3 oh nh— ^ ynh- ^ ö ^ -oh

N2- <skö> -n2 1

1 i 'o r

S0'H (° L

so h 3

When this compound was dissolved in water, a blue solution ^ max 630 nm (in 20% aqueous pyridine solution) was obtained. When this dye was used to dye cotton fibers, a blue one with excellent chlorine and wash fastness was obtained.

Examples 4-18

The procedure described in Example 1 was followed up to and with the second condensation. Then the third condensation was carried out using the third condensation component shown in the following table, whereby corresponding mixtures were obtained. The À ^ ax values of the corresponding mixtures in 20% aqueous pyridine solution are also given in the table.

35

At-sp.

Condensation component

Structural formula max

(°} ~

nh-

cooh

H0_V °) _NHYNVNH 0H OCH3 och- oh nh "/

"y"

cooh oh hn s03h s03h

so3hnh

<ê>

cooh

I - "I J

"" y "

I qn u _ _ __ Â ~ ..nh y ~ \ N ^ cu i0- (Oj) -NH-y'oY "NIJ 0 1 0

och3 ho nh '

çooh oh

N

v hn s03h s03h

è

s03h s03hNH

Cs3

cooh cooh

ìo- ^ òynh-t ^ vnh i ^ 0 0 "i x0 nh-fn v nh- / öv-oh nh gq h s03h h03s h03s nh

è 3

606nm

(Mixture)

9

660

At-sp.

3. Condensation component

Structural formula max

(o) -nhch,

cooh cooh

'- / oS-nh-f11 vnh oh och, och, h0 nh- ^ n> nh- / o) -oh ch3-n s03h s03h s03h gq h n-ch3

(e) 3è

cooh cooh

HO ^ Ô} -NH -J ^ NYNH 0 / C | UV0 ocH3 HO

VN (è ^ N2 _ ^) ^ N2 ^ èl VN

ch3 ~ n s03h s03h

h03S h03s ch3

cooh cooh

ho- <o) - nh ^ y npj çf | u n n

Y

0'SU ^ 0 NHYN YNH "^ °) ~ 0H

ch3-n s03h s03h

è

ho s h03s n 0 n

X

ch.

(Mixture)

60 5nm cooh

00 h oh och och oh nhr "ynh <0> oh c2h5-n so ^ h s03h ho3s ^ î ^ s n-c2h5

è

<° ^ hc2h5

cooh

HO ^> NH_ ^ N ^ nh O ^ C | UsO

cooh

,. w, u 9ch3 ho nh- ^ vnh ^ voh c2h5-n so3h so3h ho3s ho3s n-c2h5

è (°)

cooh ho - <q) -nh nh ö

Cu

COOH

n ° n

U A

[0XOj "2 <° H2} -> '2 J ^ V

O nhy ^ nh ^ yoh

C2H5 "F1 S03H S03h ho.

n ° n

è

h ° 3s n-c2h5

è «I

605nm i «iiche)

195

10th

At-sp.

3. Condensation component

Structural formula

, cooh c ° o'clock

HO- / ÔVNH - (^ N-NH OH 0CH3 OCH, OH NHY ^ S-NH- ^ OVOH

SO H so H "H03 ^ Hod" H

è 3 è

3 ch3

COOH

ho- <o) -nhy rv 1 / - ("- 1,.,

v o s03h s03h h03s h03s ^

ch cooh och3 oh nh -j- ^ | -nh - <q> -oh hn <$

CH.

cooh ho - \ öy nh nh 0 "c | u ^ o

. Cu cooh

O ^ CH.

so3H

h03s ho3s

(i-iisch)

cooh cooh

HO- ^ ôy NH- ^ N "YNH OH OCHj OCH3 0H NH ~ pN YNH 0H

vn n2 <ék °> -n2I5 ^] Cn

HO, S

hn och-,

so3h so3h ho3s nh

H3c ^>

• nh cooh

HO ^ ôyNHYNyNH O

och 3rd

-Cu,

X-

cooh o och3 ho nhYnYnh- (Ö> -oh

N ° N

hn

SO3H so3h s03h h03s n n nh

XH,

och-

cooh ho nh

DEAD

Cu

'O * j X \ I w

S03H S03H

eu, C00H

v 1 x0 nh - fn ynh- ^ o ^ oh n n nh so, h

3 ho, s

$

och3 (mixture)

11

660

At-sp.

■ See condensation component

Structural formula ch cooh

HO- (o) -NH m OH OCH ^ OCH3 OH NH ^ Y NIK ° / 1

n ° n ~

O O

ch hn s03h s03h cooh oh

No "<O

O O

! T °) -ch,

SO, H

n ° n

"V

nh

3 '»3

ch-

Cu cooh

HO - ^ - nh ^ Ynh x

0 och cooh ch n-v hn s03h s03h

N2- (öv / ^ yn2

3 HO NH- ^ NyNH - \ _ 0 / -OH

ho, s

ch-

O n n

V

and c NH H03S

ch3 - ^ /

620nm

, Cu

nh

"v hn so? h so, h -ch.

yN ^ NH ^ o ^ oH

n ° n cooh hoT ^ Vnh ^ N. nh 0 - ^, ^ 0 O '

N ° N r ^ S ^ N2- (öy®hN2 "fo I O ^

ch3VN "3" "" 3 "h ° 3S ho ^ rVCH3

x ° ich3 ch3-0t

/ cooh

(Mischunc

10th

^ ch3

<o) -nu2 ch3

cooh cooh ho- ^ ô) -nh y ^ nh oh och3 och3 oh nh y ^ pnh "(ô ^ oh h> ^ 2 ^ X £>» 2 ^ CN

CH30

NH S03H go H j 3

uq s ho, s MUib 3 / \ X) CH, O I 3

ch,

cooh 3rd

ho - (ÖVnh y "nvy nh rf c0

NH S03H S03H

CH.

cooh

° t »x,

ho- (q> -nh -j ^^ pnh 0

? ch3 OH NH-f ^ YN11 "(O /" 015

ho3s ho3s nh ch;

CH

3rd

cooh

Cu

N-yN I O I O

- rX

Cuv

N2 - <^ K £>

ch3o f so3h so3h s / 1-ch.

rttî

cooh nh - (ovoh

N2TOT °] V

nh h03s ho s

3 ^ y-OCH.

oh -L ° J

3 ^^ (mixture)

618nm

195

12

At-sp.

3. Condensation Component

Structural formula max

11

O> - NH,

COOH CQQh) - / ÖVnH y ^ S-NH OH OCH, OCH, OH NH-t ^ K ^ H-ToVOH

NH SO, H S03H HO, S HO, S NH

ci-C °) C ° Ld

C00H Cu 0

j / c ^ NH HH ç, | S0 OCH3 g ,, NH- | - ^ f-NH- (ô) -

V

NH SO, H SO H HO, S HO, S tfH

, COOH OH

606nm

-Cl

COOH

NH èo H SO H

«Jè 3 3 &

/ Cu ^ / -

o I o NH "Y ^ Y NH- / oV

A-M loi w

✓ ° i \

iy '. ^ so,

L-C ° 5

COOH OH

IjlH S03H

O

N

ri ^

YYH

ÈJ-C1

(i-iischunc)

COOH

COOH

HO - ^) - NH- | ^ Y-NH OH OOH3! 0CH3 OH NH-r ^ S-NH - <^> - OH

V vN

HOOC

OH

HO

COOH

so3h so3h

Cu.

ho3s I o

• COOH

OH

COOH

12

HO

- ^ C ^ -Nï COOH

PCH3? H NH-Y - '^ VNH- / ÖV OH

HOOC

S03H S03H

OH

COOH

HO- (Ö} -NH yV

NH O

O N N

NH

HOOC

, ser2

SO, H S03H

H03S H03S NH

Cu ^

CT I O NH

608nm

COOH

OH

COOH

N0- <° H O> —N

-rtr ^ -d / 0 »

OH

. • jölöj'v ho3s ho3s 5 "

S ^ "COOH OH (mixture)

13

660

At-sp.

3. Condensation component

Structural formula

13

14

<0> nh2

Ohh O

nh-

cooh cooh

HO ^ Nn-f ^ rNH OH, 0C «3 OH ^ r ^ r ™ ^ 0"

n n

V "

nh

^ s03 "so3h - ^ o ^ - nh" j ^^) - nh 0 ^ cu ho3s h03s oh cooh ho-c °)

nh i ^^^ so ^ h so3H 3

"q och3 oh nh-f ^ s-nh- / ö

V * éX ^ Nl2 ^^ N2lèà VN

3 3 a

C ^ XoH

cooh oh

6 10 nm

COOH

ho - \ öy ~ nh- | ^ y ~ nh 0- ° ^ o ^

COOH

O I O TN2 ^ °

n n V

nh 1 so h so, h ° u3

HO-t °)

cr ^ o NH-j ^ H -gy-OH

ho nh

"3 ho s x csj ^ h

(Mixture)

cooh

cooh nh s03h s03h

O

oh n

so3H SO3H

N ~ N roToi "N2 <£ X °> N2T ^ 1

NH

cooh ho- ^ ct) - nh-j ^ y- nh oh OCH3 ochj 0h nh ~ | ^ nh ~ (ô ^ - oh oh

- / ôvnh-f "y nh 0- ^ 1 ^ 0 0ch3 oh nh-r ^ s-nh- <fôvoh so ^ jso3h cooh ho

613nm

S03H SO, H NH

oh oh cooh cooh ho- ^ o \ - nh -f ^ y nh 0 ^% ft? u-o nh y '"y nh- / 0V oh nh s03h s03h so, h

V

oh so3rjs «

Oh

(Mixture)

660 195

14

At-sp.

3. Condensation component

Structural formula

15

hooc

: - <Q) -nh;

cooh ho- ^ ô ^) - nh- | ^ n'vpnh 0h n ° n ^

cooh oh

$

O cooh

0CH3 OCH- OH NH-f ^ VNH -foY-

oior «» - ^ X £) - «at§o) V

H03S H03S NH

"O

NH S03H SOjH

cooh cooh ho

Cu n n

V

^ o ° ch3

oh nh

O O

foY

COOH NH- / 0V0H

n jw so3h so3h Y

cooh h03s h03s

Y «

V

cooh cooh

HO- ^ O ^ -NH- | ^ q'n | -NH

N N

oT o

Cu cT I

N,

nh s03h s03h O '

cooh

COOH

Cu /

I ^ O NH — j ^ y-NH- ^ Oy — OH

0 ^ tsXs3V '

H03S H03S N

'o cooh (mix)

cooh cook hoh ^ nhf \ -nh oh och3 och3 0h nh -r ^ s "nh" (övoh nh s03h s03h ho3s h03s nh cx4>

cooh cooh

-NH O i O

16

H3c_ <y °) "NH2

Cl

HO- (öy NH-j ^ "y ....

cooh och3 oh nh - ^ y nh- (o ^ -oh nh s03h ho3s ho3s

Cl ch.

NH

a

CH.

Cl

COOH Cu ^ cu cooh ho- ^ ô) -nh a nh o i \> \ nh "f ^ s" nh oh h03s h03s nh O ì IO

nh s03h s03h

Cl ch.

Cl ch

3 (mixture)

15

660 195

At-sp.

3. Condensation component

Structural formula

X

Max

17th

^> NH2 • CH3

COOH cu COOH HO - ^ ÔV- NH | —NH 0 10 0 i ^ 0 NH NH - / o S — OH

s ° 3 »v CN H0> s

NH SO, H s ° 3H "O3S H0 g NH

C ° 1

CH ^ CH3

610nm

18th

(Ô> NH2

CH3

COOH COOH HO -tô \ - NH -t ^ S— NH 0 "Y? P" ^ 0 NH W NH - / ÖVoH

NH SO, H SO-H Hü3b HO, S NH éf ^ CH3

610nm

Examples 19 and 20

The procedure up to and with the second condensation was as in Example 1. Then the third condensation was carried out using the third condensation components specified in the following table, corresponding product mixtures being formed. The \ max values 35 of the resulting mixtures in a 20% aqueous pyridine solution are also given in the table.

At-sp.

3. Condensation

tionskcmpo-

nente

Structural formula cooh cooh

■ / ÖV nh oh och, och, oh- nhy tnh - / ovoh

V-V LOI, i> -, 3 _ <3 loi N— '

qn "s0 ^ h h03s h ° 3s lc9h.oh

2 4

S03H

nhc2h4oh cooh ho cooh

, och3 oh nh-f ^ f-nh ^ covoh

19th

hoc2H4NH2

- / öv-nh-f> nh 0 - ^ - 0 ,,

s03h s03h h0 ^ s ho3s nhch2ch2oh nhch2ch2oh

S03H s03H

NHCH2CH2OH

cooh cooh

H0 ^ °> NHr ^ TB "" 'TM A °' / uÌ r "T'o> NH ^ OH

HO3S'k1 ^ l nhch2ch2oh

(Mixture)

615nm

660 195

16

At-sp.

3. Condensation component

Structural formula max

20th

(hoc2h4) 2nh cooh cooh ho- / övnh nh oh och, och, oh nh "fl" nh - \ 0v0h so, h so, h ho, s ho "s T

3 "-3 *

n (ch2ch2oh) 2

3û ho, s i, j 3 n (ch2ch2oh) 2

cooh cooh h ° - ^ övnh-i ^ s- nh o '"i n0 ° ch3 oh nh y ^ s" nh / ovoh

î0® rèr ^ n2 \ ° x °) - n2t? t £ i «°»

n (ch2ch2oh) 2

so3h so3h h03s ho3s

617nm n (ch2ch2oh)

cooh cooh ho nh a nh 0-

. Cu nh> nh- / 0V0H

r tnh o 'î n9? i "0 î i0r so3h so3h n (ch2ch2oh) 2

ho, s ho, s

3 3 n (ch2ch2oh) 2

(Mixture)

Dyeing experiments a) A dyebath of the following composition was prepared from the mixture obtained in Example 1:

Dye mixture 2% of the fiber weight anhydrous Glauber's salt 10 g per liter

Bathing ratio 1:20

Cotton knitwear was placed in the dyebath. The temperature was raised to 90 ° C. in 20 minutes and the dyeing was carried out at this temperature for 40 minutes. After dyeing was completed, the knitted fabric was washed with water and then a conventional fixation treatment using 2 g per liter of a solution from “San-fix 555” (brand name for a fixative from Sanyo Kasei Kogyo KK) at a bath ratio of 1:20 at 60 ° C for 20 min, whereby a bright blue color with excellent wash and chlorine fastness was obtained, as can be seen from the following table:

Value color change stain stain from the dyed cotton silk fabric test good fabric

Wash fastness according to JIS 4-5 4 5

L-0844A-2 * (test value) (test value) (test value) chlorine fastness according to ISO-4

Method ** (test value) - -

* The dyed good was made with pieces attached to it

Silk and cotton fabrics in the presence of ten

Stainless steel balls in 100 ml of a 5% soap solution (Marseille soap) were treated at 50 ° C. for 30 minutes and the extent of the change in color of the colored goods or the staining of the adhering tissue was checked. ** The colored material was treated with an aqueous sodium hypochlorite solution under conditions which gave an active chlorine concentration of 20 ppm, a pH of 8.5 and a bath ratio of 1:10 at 25 ° C; the treatment lasted 4 hours, the extent of the color change was evaluated.

45 b) A dye bath of the following composition was prepared from the dye mixture obtained in Example 1:

Dye mixture 2% of the fiber weight (4%,

based on cotton) 50 C.I. Disperse blue 268 1.2% of the fiber weight (2.4%,

(Disperse dye for polyester fiber)

Polyester fiber)

anhydrous Glauber's salt (addition of acetic acid and 55 sodium acetate to set a pH of 5) 10 g per liter

Bath ratio 1:15

Knitted fabric made from a polyester / cotton blend (50/50) 60 was added to the dyebath. The temperature was raised to 130 ° C. in 40 minutes and the dyeing was carried out at this temperature for 40 minutes. The temperature was then lowered to 90 ° C. in the course of 10 minutes and stained at 90 ° C. for 15 minutes. After dyeing was complete, the 65-colored knitted fabric was washed with water and fixed in the manner described in dyeing test a, a blue dyeing having excellent wash and chlorine fastness being obtained, as can be seen from the table below.

17th

660 195

test

Value Color change of the colored goods

Stains from stains from cotton-silk fabrics

Wash fastness (JIS1-0844 4-5 A-2) (test value)

Chlorine fastness (ISO- 4

Method) (test value)

(Test value)

4-5

(Test value)

c) A dye bath of the following composition was prepared from the dye mixture obtained according to Example 1:

Dye mix C.I. Disperse blue 268

anhydrous Glauber's salt (adjusted to pH 5 by adding acetic acid and sodium acetate)

Bath ratio

1.4% of the fiber weight (4%, based on rayon) 1.56% of the fiber weight (2.4%, based on polyester fiber)

10 g per liter 1:15

Value color change

Staining of

Staining of the stained

Cotton

Silk fabric

Test good fabric

Fastness to washing 4-5

5

4-5

(JIS L-0844 (test value)

(Test value)

(Test value)

A-2)

Chlorine fastness 4-5

-

-

(ISO method) (test value)

Comparative tests

Comparative experiments were carried out to show that the dyes according to the invention have better washing and chlorine fastness than the known dyes. For this purpose, the dyeing test a was carried out, in each case using the dye according to the invention and using a known dye. After fixation, the wash and chlorine fastness values of the dyeings obtained were examined. The results are summarized in the following tables.

sample

Muslin fabric made of polyester / rayon (65/35) was introduced into the dyebath heated to 50 ° C. The temperature was raised to 130 ° C. in 40 minutes and dyeing continued at this temperature for 40 minutes. The temperature was then lowered to 90 ° C. in 10 minutes and stained at this temperature for 15 minutes. After dyeing was finished, the dyed muslin fabric was washed with water and fixed in the same manner as in dyeing test a, which gave a blue dyeing with excellent washing and chlorine fastness, as can be seen from the following table.

25th

30th

Authenticity comparison (test values)

Fastness to washing (A-2)

Color stain change from

Cotton fabric

Chlorine fastness (ISO)

invent

Dye of

end-

example 1

according to

(Mixture) dye from Example 4

4-5

4th

4th

(Mixture)

4-5

4th

4th

Ver

C.I.

equal

Direct blue 237 C.I.

4-5

2-

-3

2R

Direct blue 200

4th

1-

-2

2R

C.I.

Direct blue 202

3-4

2-

-3

2R

C.I.

Direct blue 109

4th

1

4-5

45 The dyes used for the comparative experiments had the following structures:

660195

18th

C.I. Direct blue 202:

HN o.

Cu

foToì- "1

- <o) - {ô / - "! nolo

NH.

so3H

SO H

S03H

S03H

C.I. Direct blue 109:

h03s "i o i o

From the table above it can be seen that none of the known dyes has both washing and chlorine fastness. In contrast, mixtures according to the invention offer excellent washing and chlorine fastness values which correspond to the market requirements.

Claims (7)

660195 2nd PATENT CLAIMS 1. Water-soluble disazo compound, which corresponds to the formula (1) in the form of the free acid n och, och- " I o 1 "ï 7" \ 3/3 0H NH I O I / Vn rr ho-s ho-s SO3H 3 3 3 'c (1) wherein X and X 'each independently represent one of the groups corresponding to the formulas (2) and (3) in the form of the free acids (5a) cooh - nh— (5 ^ oh cooh (2) so3H (3) and Y and Y 'independently represent a group corresponding to formula (5a) 20th in which Ri is hydrogen, methyl or ethyl and R2 and R3 each independently represent hydrogen, chlorine, methyl, methoxy, hydroxyl, groups of the formulas -NHC2H4OH or 25 -N (C2H40H) 2, or copper complex salts thereof. 2. Mixture containing a water-soluble disazo compound, which corresponds in the form of the free acid of the formula (1), and copper complex salts thereof. 3. Mixture according to claim 2, containing compounds 30 of the formulas (31), (32) and (33) COOH HO NH-f ® NH cooh och .. och- “/ —i 0h ^ ^ 3 oh nh-fq ^ pnh-zovoh V Î & o I S03H S03H ho-s / 3 ho3s (31) CH, COOH HO - ^ - NH. ^ ch; Cu. I / ° CIÎ3 OH NH-r '^ - rNH- / oVoH COOH n ~, n r nh S03H S03H (32) n ° n [oìoì- »2 n2 r ^ rèi Nf ho. s 3 H03S NH CH. (33) cooh f qVNH- / ÖV ° H N ^ N nh ch- 4. Mixture according to claim 2, comprising compounds of the formulas (41), (42) and (43) 660 195 cooh so3h nh o | s03h s03h ch., (41) nh ho3s ho3s ch. cooh h0 \ £ / nh fs ì — nh 0h ° \ ch3 / 0ch3 oh nh — f q> - nh / öv oh s03h cooh y '"A i ho- / ovnh - ^ \ nh o— s03h 1- | ototn2 ch- s03h s03h (42) 0ch3 oh nhy jiy "nh- ^ ov-oh n n - ( so3H cooh > n cu nh -f • "! - nh î o "ï" âl ° X 2 ^ ° nh s03h so, h (43) so3H CH " COOH ? u \ n r ~ \ | NH-r_VNH O v-OH n n— ( 0ht'21 'I S03H ho3s »o3s | 0 ch.