CH637988A5 - STABLE FINE DISPERSE AQUEOUS PREPARATIONS OF DISPERSION DYES AND / OR OPTICAL BRIGHTENERS. - Google Patents

Description

The present invention relates to stable, finely dispersed aqueous preparations of disperse dyes and / or of optical brighteners which are generally difficult to insoluble in water and which are easy-flowing and pourable.

The use of new shortened dyeing processes has increased the requirements for the finish of disperse dyes for synthetic fibers considerably in recent years. The 55 dyeing of packages in the HT range (temperature: 120 to 135 ° C.) places particularly high demands on the fine distribution and the stability of dye dispersions.

In accordance with the current state of the art, perfect, level wrapping dyeings without filtering off dye during the dyeing process can only be obtained with preparations 60 containing certain lignin sulfonates. However, these lignin sulfonates are not effective for all dyes, since the latter differ considerably in their properties, such as particle size, the particle size distribution, the hydrophilicity and - if only slightly - the solubility in water. 65 Another disadvantage of these lignin sulfonates is that these polyester fibers become very dirty during the dyeing process. This is particularly distracting when it comes to light shades or brilliant colors.

637,988

In addition, these lignosulfonates have the property of reducing sensitive azo dyes during the dyeing process; i.e. in such cases, dyeing yields which are greatly reduced are obtained.

Preparations which contain dispersants from the following classes of compounds behave very unfavorably with regard to the coloring of the winding body:

Naphthalenesulfonic acid-formaldehyde condensation products, condensation products made from cresol, 2-naphthol-6-sulfonic acid, sodium sulfite and formaldehyde (FIAT Report 1013) and sulfomethylation products as described in DE-OS 2032926 and 2301638.

With the non-ionic aqueous preparations described in DE-PS 25 02 839, it is also not possible to obtain perfect winding body colorations, since the nonionic dispersants contained in these preparations have cloud points below 120 ° C. and therefore the dispersions when heated to temperatures of

120 ° C and above are partially or completely flocculated.

The object of the present invention was to find aqueous stable and finely divided preparations of disperse dyes and / or optical brighteners which do not have the disadvantageous properties of the preparations of the prior art in the case of winding body dyeing under HT conditions.

It has been found that level wrap dyeings can be obtained without filtering off the dye or optical brightener if aqueous preparations of disperse dyes and / or optical brighteners which are sparingly to insoluble in water are used

(a) 5 to 55 percent by weight, based on a + c, of one or more finely divided disperse dyes, more optically

15 brighteners or mixtures thereof,

(b) 10 to 100 percent by weight, based on (a) a water-soluble surface-active agent of the general formula I or II

H3C-CH- / NS

f> o- (c3h60) x "(c2h40) y" (so3) z (h) 1-:

_ h3c-ch- (3rd

(Me *) ^

(I)

CH,, k

CH- ^ \

or

\ J _I W

■ \ = V0- ^ c3h60) X "(c2h4 ° ^ Y" (S03) Z (h) 1-Z (Me®) z '

CH,]

J CH-

H ^ C

(II)

wherein X = 0 to an average of 125, Y = an average of 37 to 250, where in the case of X> 37 the ratio Y: X is at least 1: 1, Z = 0 or 1 and Me® = an alkali metal ion or mixtures of these compounds ,

(c) 45 to 95 percent by weight, based on a + c, of water or a mixture of water and water retention agents and

(d) optionally contain further additives customary in aqueous dye formulations.

The liquid aqueous preparations according to the invention are low-viscosity dispersions which remain stable and low-viscosity both after prolonged storage at 25 to 30 ° C. and after storage for several days at 60 ° C. The fine distribution of the dye particles remains virtually unchanged during storage.

The new preparations are outstandingly suitable for dyeing textile material containing synthetic fibers at temperatures up to 140 ° C., in particular textile material made from cellulose esters and very particularly fiber material made from linear polyesters or mixtures of these fibers with cellulose.

With the help of the new preparations, dye baths are obtained in which the dye is stably dispersed and in which the dye is not flocculated at temperatures up to 140 ° C., even in the presence of dyeing aids that are usually used.

As disperse dyes and / or optical brighteners (a) come e.g. Dyes from 55 of the azo series, the anthraquinone series and the quinophthalone series, which are sparingly to insoluble in water, and dyes from other classes of compounds which are sparingly to insoluble in water and which absorb water from synthetic bath material, usually sparingly to insoluble in water optical brighteners or Gemi-60 see such dyes and / or optical brighteners.

The content of (a) is - based on (a + c) - between 5 and 55, preferably between 10 and 30 percent by weight.

The water soluble surfactants (b) will be 65 e.g. by reacting phenol derivatives of the formulas

637,988

4th

(ih)

(iv)

obtained with propylene oxide and subsequent reaction of the adduct with ethylene oxide or in the case X = 0 by reacting (III) and / or (IV) with ethylene oxide. If necessary, the adducts with chlorosulfonic acid or sulfur trioxide can be completely or partially converted to sulfuric acid half-esters and the resulting half-esters can be neutralized with alkaline agents.

The phenols of formulas III and IV are e.g. obtained in a known manner by reacting phenol or 2,2- (p, p'-bishydroxydiphenyl) propane with 3 or 4 mol of styrene in the presence of acid as a catalyst.

Phenols III and IV are e.g. according to known processes, first with propylene oxide and then with ethylene oxide or only with ethylene oxide in the presence of acidic or alkaline catalysts to give the corresponding oxyalkylation products (I) and (II) with Z = 0. Oxalylation can e.g. by the method described in US Patent 2979528. If X> 37, the quotient must be used

| > 1

be.

The sulfuric acid semiesters are e.g. prepared by reaction of the oxyalkylation products with chlorosulfonic acid or sulfur trioxide, the amount being able to be selected so that all free hydroxal groups or only a part is reacted (sulfated). In the latter case, mixtures of compounds of the formulas I and II are formed which contain free and sulfated hydroxyl groups. For use as surface-active agents, the half esters of sulfuric acid obtained in the reaction are converted into water-soluble salts. As such come the alkali metal salts, e.g. the sodium or potassium salts (Me® = Na®, K®) into consideration. Two equivalents are required in the case of chlorosulfonic acid, and one equivalent in the case of sulfur trioxide. As the latter, aqueous alkali metal hydroxide is expediently used. When neutralizing, the temperature should generally not exceed 70 ° C. The salts obtained can be isolated in the form of aqueous solutions or else as such and used in solid form.

The amount of (b) required depends on the one hand on the dye (a) to be dispersed and its concentration in the preparation, and on the other hand on the agent (b). In the case of dyes which are difficult to disperse or flocculate, higher amounts of (b) will be used than in the case of dyes which are readily dispersible and / or have little tendency to flocculate. The minimum amount of (b) is 10 percent by weight based on (a). In general, 30 to 200 percent by weight, based on (a), of the surfactants (b) is used. 5 Preferably, based on (a), 50 to 100 percent by weight of (b) are used.

Preparations with surface-active agents (b) in which X = 0 to an average of 2.5, Y an average of 37 to 250 and Z-0 to an average of 0.5 are preferred for technical reasons. Preparations with agents (b) in which X = 0 to an average of 2.5, Y an average of 50 to 100 and Z an average of 0.5 are very particularly preferred. Water (preferably a mixture of water and water retention agents) can be considered as constituent (ç). The water retention agents are intended to prevent the liquid preparation from drying out and crusting. As such means are e.g. Glycols and diglycols, triglycols such as ethylene glycol, di- and triethylene glycol, propylene glycol, dipropylene and tripropylene glycol, 1,2-butylene glycol or glycerol or mixtures thereof. Disinfectants, such as mold inhibitors and pH regulators, such as buffer substances and / or alkaline or acidic compounds for setting certain pH values in the aqueous phase of the dispersion. The amount of these additives can preferably be up to 2.5 percent by weight, based on the preparation.

The aqueous preparations according to the invention can be prepared in a manner known per se by dispersing or homogenizing the disperse dyes and / or the optical brighteners (a) in the presence of the water-soluble surface-active agents (b) and agents (c). The disperse dyes and optical brighteners can be used in powder form or, preferably, in the form of the press cakes obtained during production. 35 The dispersion takes place e.g. in known comminution machines, such as kneaders, ball mills, dispersers, sand mills, bead mills or attritors. The dispersion is ended when the disperse dye / optical brightener has the desired fine distribution. After the desired 40 fine distribution has been reached, the preparation is adjusted to the desired color strength.

The preparations according to the invention are further explained by the following working examples. Unless otherwise stated, the 45 parts and percentages given below refer to the weight.

The fine distribution of the preparations was characterized by the centrifugal values after the centrifugal test (Richter, Vescia; Mei-liand Textilberichte, 1965, volume 6, pages 622).

see A. Preparation of the surface-active agents (b) a1) Preparation of the phenol derivative III 312 g of styrene are placed in a 41 round-bottom flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser and heated to 50.degree. At this temperature, 684 g of 55 2,2- (p, p'-dihydroxydiphenyl) propane are introduced and 9.7 g of anhydrous p-toluenesulfonic acid are added to the suspension. After a short time, an exothermic reaction occurs, the reaction solution heating up to about 120 to 140 ° C. A clear oil results. A further 936 g of styrene are added to this reaction mixture within 60 hours at a temperature of 120 to 140 ° C. To complete the reaction, stirring is continued at 120 to 140 ° C for one hour. The product, which is very viscous at room temperature, is filled in at 70 to 90 ° C. Color of the product: red-6? brown.

a2) Preparation of the phenol derivative (IV)

94 g of phenol are melted. Then 2.03 g of p-toluenesulfonic acid are added as a catalyst and 312 g of styrene

5

637,988

roi at 130 ° C. within 4 hours with stirring. The oxyethylation product (15115 g) is added while still warm. The reaction mixture is then drained for a further 4 hours and solidifies to a colorless mass. Melting held at 130 ° C. point approx. 50 ° C.

b) oxyalkylation of the phenol obtained according to al) and a2) c) preparation of the sulfuric acid half-ester derivatives, 5 15 115 g (= 3 mol) of the ethylene oxide obtained according to b2)

bl) 1896 g (= 3 mol) of the adduct are melted in an autoclave and 349.5 g of hydroxide powder are introduced into the melt, which has been cooled to 50 to a1) and 19 g of potassium-60 ° C., at this temperature and placed in Stirring at 120 ° C. 870 g of chlorosulfonic acid were added dropwise within 10 minutes. Pressed in portions to (= 15 mol) propylene oxide, the completion of the reaction being carried out for 30 minutes at 50 to pressure not exceeding 3 bar. stirred at 70 ° C.

Then 13200 g (= 300 then the reaction mixture with approximately 50 percent mol) of ethylene oxide are pressed in at the same temperature in the same way. aqueous sodium hydroxide solution at temperatures below 70 ° C

The reaction product is neutralized warm from the autoclave (pH: 6 to 7). The product can be drained at 60 to and solidified after cooling, poured out to a colorless 70 ° C and solidifies on cooling.

Dimensions. Melting point approx. 52 ° C. 15 melting point approx. 50 ° C.

If X = 0, the yield obtained according to al) or a2) becomes 15428 g, calculated as a surface-active agent.

Reaction product only with ethylene oxide at 120 ° C below the In the same way, the reaction can also be implemented with sulfur-like conditions. trioxide can be carried out.

b2) 1896 g (= 3 mol) of the product prepared according to a1). Analogously, further water-soluble surface-active agents are produced in an autoclave with 19 g of potassium hydroxide powder 20 agent (b). These are in Tables AI and A2

mixed and put together with stirring at 120 0 C 13 200 g (= 300 mol).

Ethylene oxide pressed in portions that the pressure is not The means (b) are due to the underlying phenol,

rises above 3 bar. the amount of propylene oxide and ethylene oxide added per mole and the amount of chlorosul-25-fonic acid used per mole of adduct.

surfactant mole propylene oxide / mole X mole ethylene oxide / phenol Y mole chlorosulfonic acid / mole Z.

No phenol or adduct adduct

1

0

0

75

37.5

0

'0

2nd

0

0

100

50

0

0

3rd

0

0

125

62.5

0 '

0

4th

0

0

150

75

0

0

5

0

0

200

100

0

0

6

0

0

300

150

0

0

7

0

0

500

250

0

0

8th

5

2.5

100

50

0.

0

9

100

50

150

75

0

0

10th

100

50

200

100

0

0

11

200

100

250

125

0

0

12

0

0

75

37.5

2nd

1.0

13

0

0

100

50

1

0.5

14

0

0

200

100

1

0.5

15

0

0

125

62.5

2nd

1.0

16

0

0

300

150

1

0.5

17th

0

0

500

250

1

0.5

18th

5

2.5

150

75

2nd

1.0

19th

100

50

100

50

2nd

1.0

20th

100

50

150

75

2nd

1.0

21st

100

50

200

100

2nd

1.0

22

200

100

250

125

2nd

1.0

23

1.0

0.5

100

50.0

1

0.5

24th

2.0

1.0

100

50

1

0.5

6

H, C "

q y- ©

HG * - \ 3 "° ~~ (C3H60) X" (C2Hif0) y- (S02Na) z (H) x_z H ^ C \ = /

water soluble amount of surfactant X Y Z

Nf- = mole of propylene oxide / = mole of ethylene oxide / = mole of chlorosulfonic acid /

Moles of phenol moles of adduct or phenol moles of adduct

25th

0

100

0

26

50

100

0

27th

100

100

0

28

100

200

0

29

0

100

1

30th

50

100

1

31

100

100

1

32

100

200

1

33

10th

100

1

34

2.5

100

1

637,988

Table A2

B. dye preparations

The formulas belonging to the examples are shown on the drawing sheets. Sample and formula numbers match '.

Examples 1 to 30

11 parts of the dye of the formula see drawing sheet no. 1, Example 1 in the form of the aqueous press cake are ground with 11 parts of the surface-active agent indicated in Tables AI and A2, 10 parts of ethylene glycol and 68 parts of water until the particle size is less than 1 μm lies. Grinding time and grinding unit are given in Table I, see drawing sheet no. 2, examples 1 to 30. The preparations have a good fine distribution. The latter is characterized in Table I by the spin value. The preparations are thin and stable in storage.

Winding bodies colored with the preparations show a level coloring through the entire bobbin and no dye filtration.

Examples 31 to 50

18 parts of the dye of the formula see drawing sheet no. 3, example 31 in the form of the aqueous press cake are mixed with 9 parts of the surface-active agent given in table II see drawing sheet no. 3, examples 31 to 50, 10 parts of ethylene glycol and 63 parts of water until the particle size is below 1 | im. The dispersions obtained are thin, stable in storage and give level dyeings when dyeing packages from textured PES.

The preparations have a good fine distribution,

which are given in the form of the centrifugal values in Table II.

Examples 51 to 55 35 12.5 parts of the optical brightener of the formula see drawing sheet no. 4, Example 51 in the form of the aqueous press cake are mixed with 18 parts of those shown in Table III. Drawing sheet no. 4, examples 51 to 55 Surface-active agents, 15 parts of ethylene glycol, 4 parts of triethanol-40 amine and 50.5 parts of water are ground on the grinding unit shown in Table II until the particle size is below 1 μm.

The aqueous preparations had a good fine distribution 45, which is characterized in Table III by the spin values. The preparations are thin and stable in storage. In the case of winding body dyeing, one obtains lightened packages in any way without filtering off.

In the thermosol process, dyeings with a high degree of whiteness are obtained, after-washing is not necessary.

50

Examples 56 to 61

25 parts of the dye of the formula see drawing sheet no. 4, example 56 in the form of the aqueous press cake, with 12.5 parts of the surface active agents given in table IV see drawing sheet no. 4, examples 56 to 61, 15 parts of ethylene glycol and 47.5 parts of water are ground on the grinding unit shown in Table IV until the particle size is below 1 μm.

The preparations have a good fine distribution, 60 which are given in the form of the centrifugal values in Table IV.

Table I

Example surfactant no.

Grinder

Grinding time

Fine distribution

1

1

Ball mill

200 hours

4, 7, 24, 65

2nd

2nd

t »

? t

2, 7, 15, 76

5

3rd

tf

• f

3, 12, 28, 57

4th

4th

ff ff

2, 8, 31, 59

5

5

Sandaühle

4 passages

2i 7, 22, 69

6

6

ff ff

6, 17, 39, 38

7

7

tf ff

3, 1 *, 32, 51

S

8th

«

tf

6, 24, 42, 28

Q ✓

9

IT

tf

2, 4, 27, 67

10th

io

Glass mill

24 hours

2, 8, 27, 63

11

11

tr w

1, 5, 35, 59

12

12

«

tr

1, 12, 40, 47

13

13

tf

TT

2, 6, 20, 72

14

14

tf ff

7, 8, 36, 49

15

15

tf ff

3, 20, 41, 36

16

16

TT ff

4, 13, 29, 54

17 '

17th

«

ff

3, 12, 30, 55

18th

18th

Attritor

30 hours,

4, 16, 36, 44

19th

19th

ff ff

1, 6, 27, 66

20th

20th

ff tf

2, 4, 23, 71

21st

21st

tf tf

3, 12, 32, 53

22

22

tf tf

1, 7, 26, 66

23

23

ff ft

2, 3, 3, 92

24th

24th

tf ff

4, 13, 35, 48

25th

25th

ff ff

13, 38, 34, 15

26

26

tf tt

2, 11, 40, 47

27th

27th

• f ff

2, 2, 13, 78

28

28

tt tt

4, 6, 23, 67

29

29

ff tf

1, 5, 26, 68

30th

30th

tt

Tf

1, 5, 17, 77

637,988

QCH-

Example 31

CH0-CH0-CN

O.N- <v /> - N = N- (x /) - UC 2 \ // \ -J ^ CH2-CH2-0H

CO-CH,

Table II

Example of surface close-up aggregate grinding time fine distribution of active agent no.

31

1 .

Glass mill

24 hours

8, 26, 38, 28

3a

2nd

ff ff

5, 19, 33, 43

33

5

tf tf

U, 29, 33, 27

34

6

II

tt

10, 19, 33 ', 33

35

7

tt tf

11, 29, 37, 23

36

9

tt tf

6, 21, 35, 38

37

10th

Attritor

30 hours,

2, 20, 38, 40

38

11

tr

IT

3, 22, 35, 4Ç

39

13

11

tt

1, 10, 31, 58

40

16

»

1f

8, 32, 37, 18

41

17th

tt

Tf

9, 39, 34, 13

42

19th

ti tf

1, 5, 19, 75

43

20th

tt

It

1, 5, 1 *, 80

44

21st

ff

TT

2, 12, 26, 60

45

22

tt tf

2. 7, 31, 60

46

24th

11

It

3, 16, 39, 42

47

25th

ti

II

6, 23, 31, 40

48

26

Tt tt

3 »23, 37, 37

49

29

Tf

Tf

4, 9, 29, 58

50

30th

tf tt

8, 14, 35, 43

Example 51

637,988

= CH- ^ h-CK = CH- <

CN

Table III

Example surface active agent no.

Grinding unit grinding time * distribution of pain

51

9

Sand mill

15

Passages

13,

36,

Ol il-

9

52

13

fr

«

6,

19,

44,

31

53

16

Pearl mill i A 1O

H

3,

40,

25,

27th

54

22

tt

II

6,

14,

32,

48

55

30th

ff part

11,

0

CM

38,

31

Example 56

Table IV

Example of surface active agent no.

Grinding unit grinding time fine distribution

56

23

Pearl mill

15 h

9,

21,

37,

33

57

24th

»

»

11,

19,

35,

35

58

33

»F tr

8th,

18,

34,

40

59

34

»

tr

10,

21,

3o,

33

50

10th

Sand mill

12 passages 8,

17,

33,

42

61

13

tt

15 "

9,

19,

35,

37

Claims (10)

637 988 2 PATENT CLAIMS b) 10 to 200% by weight - based on (a) - of a water-soluble 1. Stable finely dispersed aqueous preparations of disperse surface-active agents of the general formula I sion dyes and / or optical brighteners, containing: or II ■ a) 5 to 55% by weight, based on a + c, of one or more finely divided disperse dyes, optical brighteners 5 or mixtures thereof,. H, C-CH .Yes H3c p Ä / c H- ^ C _ H3C-CH ■ ° - (C3H6 ° V (C2H4 ° V (s03) Z (H) 1-Z (Me) 22 (I) or ) y- (S0®) z (H) i_z (Me) z (II) where X = 0 to on average 125, Y = on average 37 to 250, where in the case of X> 37 the ratio Y: X is at least 1: 1. Me® = an alkali metal ion and Z = 0 or 1, or mixtures of these compounds, and (c) 45 to 95 percent by weight, based on a + c, of water or a mixture of water and water retention agents. 2. Preparation according to claim 1, comprising agents (b) in which X = 0 to an average of 2.5, Y = an average of 37 to 250 and Z = 0 to an average of 0.5. 3. Preparation according to claim 1, comprising agents (b) in which X = 0 to 2.5 on average, Y on average 50 to 100 and Z on average 0.5. 4. Preparation according to one of claims 1 to 3, containing - based on (a + c) - 10 to 30 wt .-% (a). 5. Preparation according to one of claims 1 to 4, containing 50 to 100 wt .-% (b), based on (a). 6. Preparation according to one of claims 1 to 5, characterized in that (c) contains as water retention agent ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butylene glycol, glycerol or a mixture of these agents. 7. Preparation according to one of claims 1 to 6, characterized in that it (d) contains further additives. 8. Preparation according to claim 7, characterized in that the preparation contains 0 to 2.5% (d) - based on the preparation. 9. Preparation according to claim 7 or 8, characterized in that it contains (d) disinfectants, pH regulators or a mixture of these agents. 10. Preparation according to one of claims 1 to 9, 4o characterized in that the surface-active agent (b) is in the form of the sodium salts, the potassium salts or a mixture of these salts.