DE3109954A1 - METHOD FOR COLORING HYDROPHOBIC FIBER MATERIAL - Google Patents

Description

BAYER AKTIENGESELLSCHAFT $ 5090 Leverkusen, Bayerwerk Zentralbere i

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Process for dyeing hydrophobic fiber material

Hydrophobic fiber materials, in particular polyester and cellulose triacetate fibers, have hitherto been known Dyed exclusively with disperse dyes, which have previously been subjected to an expensive mechanical fine comminution have been subjected in the presence of dispersants.

It has therefore already been proposed to dispense with this type of formation by using low-melting dispersions that are liquid under dyeing conditions. Sion dyes simply mixed together with easily biodegradable emulsifiers (cf. DE-OS 2,724,951 = U.S. Patent 4,249,902). However, such dyes are not commercially available and would have to be replaced by suitable ones chemical modification of the existing dyes can be obtained. In addition, those are too using emulsifiers comparatively relatively expensive.

That is why it has also been suggested that unformed, Resource-free, preferably commercially available

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Disperse dyes with a certain minimum solubility to be brought into a depot of a circular dyeing machine and used to dye polyester fibers under HT conditions (cf. EP-OS 00 13 892).

However, this process requires complex changes to existing dyeing machines or the development of new dyeing machines. In addition, the procurement of optimally functioning depots has so far been problematic.

Finally, DE-OS 2 330 622 discloses an isothermal process for dyeing polyester fibers with solutions of low-dispersant or dispersant-free disperse dyes have become known. Also to carry out this Special dyeing equipment is required since the dye solution is produced in a separate vessel and then must be fed into the actual dye bath at dyeing temperature. By the way, you can Here too, only special dyes with relatively good solubility in water are used, otherwise the liquor ratio is too high.

It has now surprisingly been found that at least piece goods made of hydrophobic fiber materials without difficulty under HT conditions in conventional dyeing machines without additional devices directly dye with practically informed disperse dyes can, if these dyes are in solid form under dyeing conditions, as well as a minimum solubility

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mg of 1, preferably 5 mg, per liter of the dyeing liquor comprise at 130 ⁰ C, and the dyeing machine is arranged so that both the dye liquor which can be moved to dye de material as well.

In principle, the dyes to be used according to the invention can be used without any aftertreatment the, for example in the form of the wet press cake, as it is directly in the dye synthesis accrues.

However, the dye press cakes are expediently prepared for the purpose of establishing the type conformity required in practice homogenized with the addition of small amounts of adjusting agents in a high-speed agitator mill and optionally fed to a spray dryer.

The usual aids come into consideration as adjusting agents, in contrast to conventional practice but only in amounts of 2 to a maximum of 10 percent by weight (based on pure dye) the dye press cake be added.

“Dyeing conditions” are ^{understood to mean temperatures of 120 150 °} C., pH values of 4-7 and liquor ratios of 1: 5 to 1:50.

The liquor circulation should be at least 10 l / min., Based on 1 kg of goods.

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The minimum solubility of the dyes is a natural upper limit, which results from that for disperse dyes usual absence of typical solubilizing groups, especially the sulfon-5 acid groups, results.

Dyeing machines that meet the requirements of the invention include, in particular, commercially available ones Nozzle dyeing machines and high-temperature reel skids with fleet circulation into consideration.

10 Suitable dyeing machines are in "Encyclopedia of Chemical Technology" by Kirk-Othmer, 2nd edition, Volume 8, Pages 291-294; in Melliand textile reports j_2, 1003 ff (1976) and BAYER FARBEN REVUE, No. 25, p. 37 ff (1975). Examples are:

Burlington high-temperature reel skid Krantz high-temperature reel skid Spray Jet from S. Pegg & Son, Leicester, (GB) Gaston County Jet
Giroflux from Freres, Roanne (FR) Turboflow from Obermeier, Neustadt (DE) Thenjet from Then, Schwäbisch Hall (DE) Aqualuft from Gaston, County (GB) Subtilo from Scholl (CH) R-Jet 95 from the company Thies (DE)

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The dye is generally in the form of powders, granules or aqueous dispersions at 20 - 50 ⁰ C is introduced into the dye liquor, which is subsequently heated to dyeing temperature, together with the piece goods to be dyed. The heating time does not need to be controlled.

To achieve staining that is fast to rub, it is advisable to
to subject the dyed goods to a reductive aftertreatment. Due to the lack of the usual dyeing auxiliaries and adjusting agents, this post-cleaning can, however, be carried out in the same bath, which is ^{cooled down to approx. 70 °} C. beforehand.

Compared to dyeing with conventional, A number of dyes which are rich in dispersants and finely comminuted in bead mills and the like Advantages on:

1) Cost savings by eliminating the grinding process.

2) Aids can be saved entirely or at least for the most part.

3) Foaming in the dyebath is practically impossible.

4) No staining of the dyed material due to the omission of the usual defoaming agents.

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5) Better bath exhaustion due to the (almost) complete lack of aids.

6) Less wastewater pollution.

7) Reduced dyeing times due to the omission of the heat-up 5 steering.

8) Easier aftercare.

The new process is explained in more detail with the aid of the following examples, without, however, being restricted thereto.

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example 1

(. CI 63285) 3 g (0.6%) of the only coarsely ground, but not otherwise-formed disperse dye Disperse Blue 56 (water solubility at 130 ⁰ C: 14 mg / 1; 5 ^ mp 200 ⁰ C.) Are, together with 7 1 cold water and 500 g of textured polyester knitted fabric are introduced into a Mathis laboratory jumbo jet and, within 30 minutes, the liquor is constantly circulated at 6 l / s and a fabric speed of approx. 20 m / min, inside

^10/2 heated 30 minutes continuously at 13O ⁰ C. At this temperature, dyeing is carried out for a further 50 minutes with constant movement of the liquor and goods, then ^{cooled to 70 °} C. over the course of 20 minutes and, after adding 3 g / l of sodium hydroxide solution

38 ° Be and 1.5 g / l hydrosulfite for 10 minutes in the same liquor reductively cleaned. After the liquor has been drained off, it becomes 60% with 2-3 ml of acetic acid acidified and then rinsed cold. After spinning, drying and calendering, a full-Ie is obtained Blue staining in 1/1 RTT, the shade fuller than 2.2% staining with commercially available CI. Disperse Blue 56 and which does not differ in the known good fastness properties.

If the textured polyester knitted fabric is replaced by appropriate amounts of cellulose triacetate fabric and If you otherwise proceed as described in the example, you will get colorations with equally good results.

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AO

Example 2

A disperse dye combination

a) 37.5 mg (0.0075%) Disperse Yellow 60 (CI. 12 712)

(Solubility in water at 13O ⁰ C: 58 mg / 1) and

b) 27.0 mg (0.0054%) of the dye of the formula

(Water solubility at 130 ⁰ C: 4 mg / 1) and

c) 25.5 mg (0.0051%) Disperse Blue 56 (CI. 63 285)

(see example 1)

are dyed under the same conditions as described in Example 1 on textured polyester material. After cooling to 7O ⁰ C, the colorless liquor is discharged hot without reductive purification of the intermediate color and the dyed material is calendered after spinning and dried.

An absolutely level light gray dyeing with perfect dry and wet rub fastnesses is obtained.

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Example 3

A disperse dye combination consisting of

a) 4 g (0.8%) of the dye of the formula

Cl

(X ₃ N - <^ VN -NC C- CH,

² \ = / Il Il ³

HO-C N

Melting point:> 200 ⁰ C ° 2 ^£
(Water solubility at 130 ⁰ C: 249 mg / 1)

b) 5.5 g (1.1%) of the dye of the formula

<f / - ^N ■ N 4! VN

Ό C ₂ H ₄ COCH ₃

Melting point: approx. 125 ^° C
(Water solubility at 130 ⁰ C: 187 mg / 1)

c) 1.25 g (0.25%) of the dye of the formula

NO ₂

CN NHCOCH ₃

Melting point: approx. 205 ^° C
(Water solubility at 13O ⁰ C: 5.5 mg / 1)

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* · ♦ · ■ m

-to -

is dyed and aftertreated as described in Example 1. A uniform, dark brown color is obtained
Dyeing with excellent fastness properties.

If, instead of the dyes or dye combinations mentioned in Examples 1-3, which are used in The dyes listed in the table below give level dyeings with otherwise identical procedures with mostly slightly higher depths of color than with disperse dyes found with the same coloring method and raw dye input can be obtained.

(RTT = standard depth) Le A 20 929

Tabel

example

RTT in %

Constitution melting point

Water solution
opportunity
at 130 ^° C

nuance

0.7

> 200 ⁰ C

21mg / l

Brill.

greenest.

yellow

0.6

_X CN H, CO-C- ^ Vc-OC ₂ H ₄ -N- ^ V CH = C

Ö CoH ^ ^X CN

approx. 130 ⁰ C

35mg / l

greenest.
yellow

ι ·

1? ^:

I »·

CH,

0.16

f V SO ₂ O

ff Vn = ν

HO

CN about 200 ⁰ C

20mg / l

greenest.
yellow

1.95

about 150 ^u C

121mg / l

NO neural
yellow

co

ο co co cn

cb table

at
game RTT
in % 0 ₂ N < constitution N - / "Vl C ₂ H ₄ OCONHCH ₃ ) ₂ Enamel
Point Water sol
opportunity
at 130 ^° C nuance β Br
3 Cl θ 0.8 "Vn = ν
= / about 170 ° C 65 mg / 1 Brown O ₂ N -i \
Br "Q- H (C ₂ H ₄ OH) ₂ Br
S. CH ₃ 9 0.7 0
If about 150 ⁰ C 229mg / l Brown O ₂ N ^ ^ Br N (C ₂ H ₄ OCOCH ₃ ) 2 Cl 10 0.7 ^ C ₂ H ₄ CN : a.130 ° C 80mg / l Brown O ₂ N ^ / Cl ^ C ₂ H ₄ OCOCH ₅ Cl
- < 11 0.7 J N = N about 200 ⁰ C 130mg / l Brown Cl

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Tabel

at
game RTT
in 96. constitution Enamel
Point Water sol
opportunity
at 130 ° C nuance 12th 0.6 .C ₀ H. CN
0 Nf VN = N -f \ V- N
\ = <\ = / ^ C ₀ H ₁ -CO ₀ CH,
CN. ^{2 4 2 3} approx. 150 ⁰ C 150mg / l Red 13th 0.6 O ₂ NAN = N - / "Vn (C ₀ HaOCOCH,) ₉
CN approx. 130 ⁰ C 95mg / l Red 14th 0.6 ON- / Vh = NV V ^n
ά V = / W / ^ C ₂ H ₄ OCONH
CH C ₄ H ₉ 2a.15O ° C 82mg / l Red 15th 0.5 OH
^ ~ y ν ₌ ν - ^ ~ V ⁿ = ⁿ - \ S
R = 50% H ^ -f
50% COCH ₃ SO ₂ NC ₂ H ₄ OR about 200 ⁰ C 91mg / l Red

Tabel

at
game RTT
in % constitution Enamel
Point Water sol
opportunity
at 130 ^° C nuance 16 0 »9 0 NH ₂ ο
fi ^{; i} "V ' ^v V ^l V 0-C ₉ HyOCOR
I j »I 1 4— * t
0 OH R = C ₂ H ₅ ; C ₅ H ₅ about 20O ⁰ C 30mg / l Brilliant-
Red 17th 1 »2 0 NH ₂
^ y ".. Av-o (ch ₂ ) ₆ oh
Il '
0 OH about 150 ° C 102mg / l Brilliant-
Red 18th 0.33 NN
^H 5 ^C 2 ^SSN = ^N -O " ^{N (C} 3 ^H 7 ^{) 2} ·
NHCOCH ₃ about 120 ⁰ C 75mg / l bluest.
Red 19th 0.53 _y C ₂ H ₄ CN
° 2 ^N \ / ~ ^{N = N} \ / ^N
\ '* CoH / OC OCH · »
CN ^ά * *. about 20O ⁰ C 45rag / l ruby

• c t t

tr * table

at
game RTT
in % constitution Enamel
Point Water sol
opportunity
at 130 ^° C nuance 20th 1.0 O NH ₉ O
ι ι ·
Π LI N (CHg) ₃ -OCH,
t * »
0 HH ₂ 0 about 180 ° C 72mg / l brilliant
blue 21st 1.0 0 NH ₉
j ^ i ^^ r ^ V ^ V- SO ₂ O- ^ J)
ö k ₂ 180 ⁰ C 55mg / l blue 22nd 0.8 OH 0 OH
NH ₂ O NH ₂ > 200 ⁰ C 24mg / l blue 23 CN
O ₂ NHf ^ -N = Ν- / Λ-Ν (C ₂ H ₅ ) ₂
^CN NHCOCH ₃ > 200 ° C 5mg / l blue

Tabel

example

RTT in %,

Constitution melting point

Water solubility at 130 ⁰ C

nuance

24

0.8

OH 0 NH ₂

X: approx. 40 * H approx. 60 -J ₀ CH

about 200 ⁰ C

17mg / l

blue

25th

26th

0.6

1.0

N = N nTy N (C ₂ H ₄ OH) ₂ NHCOCH,

NO

OCH

O ₂ N

n = ν - / V-N

about 150 ° C

214mg / l

> 200 ⁰ C

105 mg / 1

greenest. blue

Dark blue

Tabel

at
game RTT
in % constitution Enamel
Point Water sol
opportunity
at 130 ° C nuance 27 1.77 - NO ₂ OCH _{3 o}
O ₂ N- / Vn = N- / VN (C ₂ H ₄ OCOCH ₃ ) ₂
Br NH
COCH ₃ about 140 ° C 30mg / l marine
blue 28 0.6 O ₂ NI ^ A ₁ / ^ C ₂ U ₅
N = N -F ^ -Vl '
"^ C ₂ H ₄ OCOCH ₃ approx. 120 ⁰ C 92mg / l rotst.
blue 29 0.9 Br OCH,
0j / \ - N = N ■ // \ _ _N ( _C2 h ₄ 0C0CH ₃ ) ₂
NO ₂ NHCOCH ₃ approx. 145 ° C 62mg / l marine
blue 30th 1.8 Br / °° ^Κ 3 Ο
° 2 ^N "v3 ~ ^{N = N} ■ / ^ ^r - ^NHC 2 ^H 4 ^ ^0C 2 ^H 4 ^0CH 3
^N0 2 NHCOCH ₃ about 200 ⁰ C 90 mg / 1 marine
blue

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Tabel

example

RTT in

Constitution melting point

Water solubility at 130 ^° C

nuance

31

0.8

CN

= N Y

/ ^C 2 ^H 5

CN

CH,

C ₂ H ₄ OCONHCH ₃

> 200 ⁰ C

84mg / l

blue

32

1.1

CN

N = N - / "VN (C ₂ H ₅ )

NO.

2 ¹ V

NHCOCh ₂ OCONHCH ₃ > 200 ⁰ C

78mg / l

Navy blue

33

0.6

O ₉ N 4 \ - N = N - / Λ- Ν η

^CN

^ C ₂ H ₄ -C-OGH ₃

a 200 ⁰ C

NHC-CH, H -> O purple

CD CO CO

Claims (8)

Claims 1. Process for dyeing piece goods made of hydrophobic Fiber material under HT conditions with conventionally unformed disperse dyes, characterized in that a) these dyes are present in solid form under dyeing conditions and a minimum solubility of 1 mg, preferably 5 mg, per liter of dye liquor having at 13O ⁰ C, b) these dyes are introduced directly into the dye bath and c) the dyeing machine moves both the dye liquor and the material to be dyed. 2. The method according to claim 1, characterized in that the dye is in the form of the wet Press cake, as it is obtained in the synthesis, uses. 3. The method according to claim 1 and 2, characterized in that the dye by addition of a maximum of 10 percent by weight of thickener, adjusted dye press cake according to type, if necessary after spray drying. Le A 2Q 929 4. The method according to claim 1, characterized in that the dye at 20 - 50 ⁰ C is introduced into the dye liquor and these are then heated to high dyeing temperature. 5. The method according to claim 1, characterized / that a nozzle dyeing machine is used as the dyeing machine. Process according to claim 1, characterized in that the liquor circulation is at least
10 l / min, based on 1 kg of goods. 7. The method according to claim 1, characterized in that that one subjects the dyed goods to a reductive aftertreatment and this in the same Dye bath makes. 15th 8. The textile materials dyed according to Claims 1 to 7. Le A 20 929