DE1220825B - Reducing agent for dyeing and printing textiles - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

D 06p

German class: 8m- 3/01

Number: 1220 825

File number: B 61087IV c / 8 m

Filing date: February 1, 1961

Opening day: July 14, 1966

When dyeing and / or printing textiles with vat and / or sulfur dyes the reducing agent used in an alkaline medium is usually sodium dithionite or its derivatives of alkanesulfinic acids.

In the literature, for example in British Patent 829 936 or in German Auslegeschrift 1061739, the alkali metal, alkaline earth metal, dizinc or ammonium salts of straight-chain or branched hydroxyalkanesulfinic acids with 1 to 4 carbon atoms are mentioned as reducing agents, and in German Patent 1086 209 and in German Auslegeschrift 1071042, compounds of the general formula are used as reducing agents in dyeing and printing
of textile goods

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Adolf Blum,

Dr. Günter Meyer, Ludwigshafen / Rhine

mentioned as reducing agent, where A is a hydrogen atom or a low molecular weight alkyl radical means which in turn is a radical of the general formula as a substituent

/ (H) ₁

II

can carry, where D in formulas I and II represents the remainder of a salt of an alkanesulfinic acid with 1 to 4 carbon atoms of the general formula

C-SO ₂ ⁹ Z®

III

and where χ is one of the numbers 0, 1 and 2, y is one of the numbers 1, 2 and 3 and (x + y) is the number 3. In formula II, each of the values ρ and q can stand for one of the numbers 0, 1 and 2, where (p + g) always denotes the number 2. In the formula III, each of the radicals E and G can represent a hydrogen atom or an alkyl radical, and Z® denotes the cationic radical of an alkali or alkaline earth metal or of ammonium.

Furthermore, it is from the literature, for example from the German patent specification 1004188, known, the formamidine sulfinic acid (also aminoiminomethanesulfinic acid or called thiourea dioxide) in an alkaline medium instead of sodium dithionite or hydroxymethanesulfinic acid Use sodium as a reducing agent.

The above-mentioned reducing agents, which differ from one another in that they are ^{more or less stable at temperatures between approximately 10 and 35 °} C. (ie have a more or less high redox potential), in particular the water-soluble reducing agents, can be used for dyeing and / or printing of textile goods, such as fibers, threads, flocks, woven and knitted fabrics, preferably made from native and / or regenerated cellulose, but also made from natural silk or from linear synthetic polyamides. In addition, the reducing agents mentioned are used for dyeing and / or printing mixed fabrics or mixed webs, for example made of natural and synthetic fibers, such as cotton and linear aromatic polyesters, ζ. B. polyethylene glycol terephthalate, or based on terephthalic acid and p-dimethylolcyclohexane can be used. If the abovementioned reducing agents are sparingly soluble in water, they can also be used for printing and / or etching textiles.

In dyeing, sodium dithionite is generally preferred as the reducing agent, while the other compounds of the aforementioned type are preferably used as reducing agents when printing be used. The application of the

609 589/282

3 4

Reducing agent is usually used in dyeing, compounds of the general formula
apart from the so-called pigment block process,
in an aqueous alkaline medium. The so-called

The reduction y is used for direct printing
medium together with an alkaline 5. (D) ₂ ,
Agent of the printing paste containing a thickener and the dye, and in the case of A, D, x, y and (x + y) the above mentioned two-phase printing process, the good will have meaning, is obtained in various ways in the first stage one way containing the dye, e.g. B. by printing on ammonia or the printing paste and then in a 10 on derivatives of ammonia, which is treated with the reducing agent via stick second stage. bonded to the substance carry at least 1 hydrogen atom, since the various dyeing or printing alkali metal salts, such as the sodium and potassium processes, have different requirements on the reducing salt to be used, or alkaline earth metal salts such as the calcium agent and the barium salt or ammonium salts of the and none of the named reducing agents 15 straight-chain or branched hydroxyalkanesulfinic meets all requirements, it is customary to use acids with 1 to 4 carbon atoms, which, depending on the intended use, carry the sodium dithionite hydroxyl group and the sulfinic acid group on or offspring of alkanesulfinic acids of the same carbon atom above, as the type mentioned hydroxy as reducing agent in alkaline methanesulnic acid, the 1-Hydroxyäthansulfinsäure- (1), medium to choose. In this prior art 20 of 1-hydroxypropanesulfinic acid- (1), the 2-hydroxy was to look for reducing agents which act in propanesulfinic acid- (2) or the 1-hydroxy-normal alkaline medium the advantages of the different butanesulfinic acid- (1) leaves. Conventional reducing agents can be combined with one another, including salts of various hydroxyalkyl bonds, without the disadvantages caused by the anesulfinic acids having 1 to 4 carbon atoms or the use of these reducing agents, all at once or in any order. Versatile reducing agents based on ammonia or on. The above-mentioned should therefore be allowed to act in the temperature range between 10 compounds of ammonia. .
and 35 ⁰ C (ie they should be in complexes of alkali metal cyanides. of chromium, of this range by a redox manganese as low as possible, cobalt and nickel are exemplary potential), but at temperatures 30 wise the compounds of the formulas
be capable to 100 ⁰ C (ie at temperatures between about 90 and 110 ⁰ C), vat and / K ₃ [Cr (CN) _6],
or sulfur dyes in the shortest possible time K3 [Mn (CN) 6],
to reduce (ie, they should have as high a redox potential as possible at these temperatures- 35 K ₄ [Mn (CN) ₆ ],

ben). K ₂ [Ni (CN) ₄ ] -3 H ₂ O,

It has now been found that reducing substance mixtures which have a content of (a) K ₃ [Co (CN) ₆ ],
Descendants of preferably 1 to 4 carbon KU [Co (CN) ₆ ],
Alkanesulfinic acids containing atomic atoms and (b) 40

as redox catalysts complex alkali metal cy- Na ₂ [Ni (CN) ₄ ] ^ H ₂ O,

anides of chromium, manganese, cobalt and Na ₄ [Mn (CN) ₆ ]

or or of the nickel. in alkaline _unc [

Medium as reducing agent in dyeing and Na ₃ [Mn (CN) G].
Printing of textile goods are versatile. 45

Descendants of preferably 1 to 4 carbon- Further redox catalysts of the aforementioned

Alkanesulfinic acids containing atomic atoms are of the type ^{sin (} ^

for example. especially the alkali metal, earth K ₃ [Mn (CN) ₅ NO],

alkali metal or ammonium salts of straight · Na ₂ [Ni (CN) ₃ NO],

chain or branched hydroxyalkanesulfinic acids 50. :

with 1 to 4 carbon atoms and advantageously K ₄ [Co (CN) SCO],

Compounds of the general formula K ₃ [Cr (CN) SNH ₃ ],

AK) _x K ₃ [Co (CN) ₅ NO ₂ ],

** (■■ - L 55 Na ₅ [Mn (CN) ₅ SO ₃ ].
XD)

The new reducing substance mixtures where A, D, x, y and (x + y) have the treatment baths indicated above or the treatment baths, for example dyeing and bleaching baths, and also the form bleaching baths, appropriately contain the derivative amidinesulfinic acid. 60 pieces of preferably 1 to 4 carbon atoms

As alkali metal, alkaline earth metal or ammo- containing alkanesulfinic acids and the previously genium salts of straight-chain or branched Hy- named redox catalysts in a mixture of hydroxyalkanesulfinic acids for example, let the ratio of. 0.1 to 10P / 6 redox catalyst, trium, potassium, calcium, barium or ammonia based on the weight of the derivative salt the hydroxymethanesulfinic acid, the 1-hy- 65 lings of preferably 1 to 4 carbon atoms droxyäthansulfinsäure- (l), the 1-Hydroxypropansul- containing alkanesulfinic acids. You can finsäure- (l), the 2-hydroxypropanesulfinic acid- (2) or new mixtures of substances also on the with it, too called the l-hydroxy-n-butanesulfinic acid- (l). to be treated, for example

by first printing a textile fabric with a printing paste that is the descendant of a preferably contains 1 to 4 carbon atoms containing alkanesulfinic acid, and then the printed Tissue treated with an aqueous solution containing a redox catalyst of the type mentioned above contains. When preparing the new reducing substance mixtures you can also use Mixtures of two or more descendants of preferably 1 to 4 carbon atoms Alkanesulfinic acids and mixtures of two or more of the aforementioned Redox catalysts run out.

The reducing substance mixtures according to the invention make it possible to use them as a reducing agent for dyeing and / or printing textile goods with vat and / or Sulfur dyes a significant reduction in the reduction time (usually the reduction speed is doubled when printing one per kilogram of printing ink in the presence of 1 to 2 g of a redox catalyst of the abovementioned Type and the corresponding amount of reducing agent works) and thus a larger production per time unit. In addition, when using the new reducing substance mixtures for the reduction of vat and / or sulfur dyes in an alkaline medium a lower one Amount of derivatives of alkanesulfinic acids, preferably containing 1 to 4 carbon atoms needed than if one contained the sulfinic acid derivatives contained in the new reducing substance mixtures without the addition of redox catalysts of the above type alone as reducing agents used. The combination according to the invention and the combined use of the reducing agents and the catalysts therefore meet a real need of printing and dyeing technology; you can however, they can also be used to advantage for bleaching textiles and other substrates.

The application of the reducing substance mixtures, which are still further for the use may contain desired or necessary auxiliaries, according to the invention and the thereby The technical advances achieved are illustrated in the following examples.

The parts and percentages given in the examples are weight units.

example 1

Cellulose tissue is printed with the following printing paste:

300 parts of a 5% locust bean gum ether thickener,

300 parts of a 10% strength ether thickener, 80 parts of a 20% strength aqueous dough of the

Dye C.I. Vat Blue4 (Color

Index. 2nd Edition. 1956, Vol. 2, p. "2494.

C. I. No. 69 800), ..

320 parts of water, ■■

(α) 50 parts of the compound of formula

CH ₃

O ₂ S · HCv
O ₂ S · HC /

CH ₃

CH ₃
CH'-SO ₂

ΘΘΘ

3 Na © IV

90 parts of an aqueous sodium hydroxide solution 38 ° Be,

15 parts of sodium tetraborate,
845 parts of water,

1000 parts. :

After printing and drying, part of the item is with the help of the following solution a two-roll poulard prepared.

1000 parts.

The fabric is then steamed in air-free steam for 30 seconds at 115 ° C. without drying in between and finished in the usual way. A blue print is obtained on a white background.

Another part of the printed and dried fabric is made with the help of a two-roll pad impregnated with the following solution containing a new reducing substance mixture:

{ß) 35 parts of the compound of formula IV,
2 parts of the compound of formula

K ₄ [Co (CN) ₆ ],

90 parts of an aqueous sodium hydroxide solution 38 ° Be,

15 parts of sodium tetraborate,

858 parts of water,
1000 parts.

The fabric impregnated with this solution only needs ^{to be steamed for 15 seconds at 115 °} C. in air-free steam without intermediate drying in order to produce a bright blue print on a white background.

The comparison shows that when using the new reducing substance mixture [solution (β)] 30% less compound of the formula I is required than when using solution (α) and that only when using solution (β) to fix the dye half as long steaming time is required as when using solution (α). Instead of 80 parts of a 20% strength aqueous dough of the dye CI Vat Blue 4 - (Color Index, 2nd edition, 1956, vol. 2, p. 2494, C I. No. 69800), 80 parts of a yellow one can also be used Sulfur dye, e.g. Use BCI Sulfur Yellow 5 (Color Index, 1956, Vol. 2, p. 2365). In this case. you get a yellow print on a white background.

Example 2

Cotton fabric is printed with the following printing paste:

(α) 20 parts of the dye CI Vat Red IO (Color Index, 2nd edition, 1956, vol. 2, p. 2460, CI No. 67,000),
60 parts of thiodiglycol,
600 parts starch-tragacanth thickening,
120 parts of potassium carbonate,
80 parts of the compound of formula

[H ₂ N-CH ₂ -SO ₂ pNa® V
120 parts of water,

1000 parts.

After printing and drying, the material absorbs in a star damper for 15 minutes in air-free steam at 100 ⁰ C. and the red print in a conventional manner by rinsing and oxidizing finished.

If the following, a reducing substance mixture is used instead of the printing paste (α) according to the invention containing printing paste:

(ß) 20 parts of the dye CI Vat Red 10, 60 parts of thiodiglycol,
600 parts starch-tragacanth thickening,
120 parts of potassium carbonate,
80 parts of the compound of formula V,
1 part of the compound of formula

Na ₂ [Ni (CN) ₄ ] • 3 H ₂ O
119 parts of water,

IO

20th

1000 parts.

and if the rest of the procedure is as explained above, you need to fix the dye in place 15 minutes only has a steaming time of 8 minutes.

B e i s ρ i e 1 3

Precleaned and dried raincoat poplin fabric is made with the following slurry by means of a commercially available three-roll pad (with a squeezing effect of 75%) padded and dried:

35 parts of C.I. Vat Brown 44 dye

(Color Index, 2nd edition, 1956, Vol. 2,

P. 2548, C.I. No. 70 802),

965 parts of water,

1000 parts.

The padded fabric is then treated with the aid of a two-roll pad (squeezing effect 80%) with the following solution:

(α) 100 parts of aqueous sodium hydroxide solution

38 ° Be,
60 parts of the sodium salt of 1-hydroxyethane sulfate

fic acid- (l),
30 parts of sodium sulfate,
810 parts of water,
1000 parts.

The product is then passed through a continuously operating steamer, in which the brown dye is fixed by steaming at 115 ° C for 45 seconds. The material to be dyed is now more usual Way finished.

If the following, a new reducing substance mixture is used instead of the solution (α) containing solution:

(ß) 100 parts of aqueous sodium hydroxide solution

38 ° Be,
60 parts of the sodium salt of 1-hydroxyethane sulfate

fic acid- (l),
1 part of the compound of formula

Na ₄ [Mn (CN) ₆ ],

30 parts of sodium sulfate,
809 parts of water,

and if the rest of the procedure is as explained above, it is necessary to fix the brown dye only a steaming time of 30 seconds.

Another advantage of this process is that there is no dye peeling in the chemical pad entry.

Example 4

A fabric made of so-called two-and-a-half acetate fiber is diazotized with 3% of that by coupling 1-amino-4-nitrobenzene with 1-dihydroxyethylamino-3-methylbenzene available azo dye and then printed with the following printing paste:

(α) 30 parts of Bz-1-methoxybenzanthrone,
30 parts of sodium benzylsulfanil,
100 parts of calcium salt of hydroxymethanesul-

fic acid,

60 parts of polyethylene glycol,
50 parts triethenolamine,
500 parts crystal rubber thickening 1: 2,
230 parts of water,
1000 parts.

After printing and drying, the item is steamed for 10 minutes and finished as usual. A green etched print on a red background is obtained.

If the following, a new reducing substance mixture is used instead of the printing paste (α) containing printing paste:

(ß) 30 parts of Bz-1-methoxybenzanthrone,
30 parts of sodium benzylsulfanil,
100 parts of calcium salt of hydroxymethanesul-

fic acid,
1 part of the compound of formula

K ₃ [Ni (CN) ₄ ] • 3 H ₂ O

60 parts of polyethylene glycol,

50 parts triethenolamine,
500 parts crystal rubber thickening 1: 2,
229 parts of water,

1000 pieces,

1000 pieces,

and if the rest of the procedure is as explained above, only a steaming time of 5 minutes is required.

Example 5

Cotton fabric is printed with the following printing paste:

(α) 150 parts of 4,4 ^/ -dimethyl-5,6,7'-trichlorothioindigo

(20%),

600 parts of a 5% locust bean gum ether thickener,

250 parts of water,
1000 parts.

After printing and drying, the product is placed on a two-roll pad with the following solution impregnated:

(γ) 80 parts of the sodium salt of hydroxymethanesul-

fic acid,

80 parts of aqueous sodium hydroxide solution
■ 65 38 ° Be,

15 parts of sodium tetraborate,
825 parts of water,
1000 parts.

1 2120

The fabric is now steamed in air-free steam at 115 ^° C. for 4 minutes. A blue print is obtained on a white background.

If one uses the following instead of the solution (α), a solution containing a reducing substance mixture according to the invention:

(ό) 80 parts of the sodium salt of hydroxymethane sulf

fic acid,
1 part of the compound of formula

.

, K ₃ [Co (CN) ₆ ],

80 parts of aqueous sodium hydroxide solution

38 ⁰ Be, ι

15 parts of sodium tetraborate,

824 parts of water,

1000 ^parts:

or the following printing paste is used instead of the printing paste (α)::,

(β) 150 parts of 4,4'-dimethyl-5,6,7'-trichlorihioindigo

(200 / oig),
600 parts of a 5% carob bean gum

ether thickening,
1 part of the compound of formula

K ₃ [Co (CN) ₆ ],

25th

249 parts of water,

30th

35

1000 pieces,

and if the rest of the procedure is as explained above, one needs. _; instead of 4, minutes only, 1 minute for steaming. _{i (} ,;

ι. \ Example 6, ._. ·, ._

: Cellulose tissue is made with 2% of the red direct dye CI. Direct Red 79 (Color Index, 2nd Edition, 1956, Vol. 2, p. 2103, C.I. No. 29 065) colored and printed with the following printing paste:

(α) 300 parts of a 5% carob bean gum

ether thickening,
• '-300 parts of a 10% starch ether, 20 parts of the dye CI Vat ^: Green I

(Color Index, 2nd edition, 1956, Vol. 2, p. 2519, CI. No. 59 825), 80 parts of fomamidinesulfinic acid, 300 parts of water,. ■

1000 parts. '-. '. ■ "',

After printing and drying, the goods are covered with the help of a two-roll pad with the following, Solution prepared:

100 parts of sodium carbonate, 15 parts of sodium tetraborate, 885 parts of water,

1 part of the compound of formula

K ₃ [Mn (CN) ₆ ],: '■

80 parts of formamidinesulfinic acid, 299 parts of water,

1000 parts,. . . :

or instead of the solution (γ) the following solution:

(ö) 100 parts of sodium carbonate, 15 parts of sodium tetraborate, 1 part of the compound of the formula

K ₃ [Mn (CN) ₆ ], 884 parts of water, ■.

1000 pieces,

and if you proceed as previously explained, only a damping time of 30 seconds instead of 1 minute is required. < ■■ - · ■ '

For example, 7

Instead of the reducing material mixture described in Example 4 according to the invention, the following mixtures ^ can be ^used::.

A. 93% calcium salt of hydroxymethanesulfinic acid 7% of the compound of the formula

K ₃ [Co (CN) ₆ J B. 92% of the compound of the formula

55

1000 parts.

The fabric is then steamed at 110 ° C. for 1 minute without drying in between. You get one green print on red background.

If you use the following, a new reducing substance mixture instead of the printing paste (α) containing printing paste:

(ß) 300 parts of a 5% carob bean gum

ether thickening,

300 parts of a 10% strength starch ether, 20 parts of the dye CI Vat Green I, [H ₂ N-8% of the compound of the formula Na ₂ [Ni (CN) ₄ ] -3 H ₂ O

and instead of the reducing substance mixture according to the invention described in Example 6 the following mixture can also be used:

C. 97% formamidinesulfinic acid 3% of the compound of formula

K ₃ [Co (CN) ₆ ]

The following new mixtures can be used instead of the reducing substance mixtures described in Examples 1, 2, 3 and 5 ″ according to the invention:

D. ' 98% of the compound of the formula

HO · CH ₂ · SO ₂ · Na 2% of the compound of the formula K ₃ [Cr (CN) ₆ ]

E. 99% of the compound of the formula H ₃ C • CH • SO ₂ • Na

OH

1% of the compound of the formula

Na ₂ [Ni (CN) ₄ ] • 3 H ₂ O

. ·;! ■:. :: 609 589/282

F. 96% of the compound of the formula

O ₂ S • CH ₂ S
O ₂ S · CIV

) N ■ CH ₂ ■ SO ₂

ΘΘΘ

3 Na®

4% of the compound of the formula

Na ₃ [Mn (CN) ₆ ] G. 98% of the compound of the formula

CH ₃

O ₂ S · CHs
O ₂ S

L. 97% of the compound of the formula.

/ H Πθθ

^ CH ₂ · SO ₂

/ CH ₂ · SO ₂

^X N (

C <

2 Na®

CH ₃ ) N - CH • SO ₂

CH ₃
2% of the compound of the formula

Na ₂ [Ni (CN) ₄ ]

H. 96% of the compound of the formula

θθθ

3 Na®

3% of the compound of the formula K ₃ [Cr (CN) ₆ ]

M. 99.8% of the compound of the formula

H ₃ C • H ₂ Cn

CH ₂ • CH ₂ • CH ₃

) N - CH · SO ₂

K®

O ₂ S-CH _2x

N-CH ₂ -CH ₂ -N

/ CH ₂ -

ΘΘ

2 Na®

4% of the compound of the formula

K ₃ [Cr (CN) ₆ ]

J. 99.5% of the compound of the formula H ₃ C • CH ₂ -CH-SO ₂ -K

OH 0.5% of the compound of the formula

Na ₃ [Mn (CN) ₆ ] K. 99% of the compound of the formula

H ₃ Cs

> N-CH-SO ₂ CH ₃

Na®

0.2% of the compound of the formula K ₃ [Co (CN) ₆ ]

Claims (1)

Claim: Use of mixtures of substances with a content of a) derivatives of alkanesulfinic acids preferably containing 1 to 4 carbon atoms and b) complex alkali metal cyanides of chromium, manganese, cobalt or nickel as redox catalysts as a reducing agent when dyeing and printing textiles. 1% of the connection Na ₃ [Mn (CN) ₆ ]
When the application was announced, three coloring tables were laid out. Considered publications: German Patent No. 874,759; French Patent No. 1,100,992; U.S. Patent No. 2,690,952. 609 589 / 2S2 7.66 θ Bundesdruckerei Berlin