DE2930541A1 - METHOD FOR PRODUCING RESERVE EFFECTS ON MIXED MATERIALS MADE OF POLYESTER AND CELLULOSE FIBERS - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT HOE 79 / F 207 Dr.KL / cr

Process for the production of reserve effects Mixed materials made from polyester and cellulose fibers

The direct printing on mixed materials made of polyester and cellulose fibers is known to be difficult tied together. Because pigment printing is not satisfactory in every respect, and so is printing with mixed dye systems Raises problems, special disperse dyes have already been developed, which can be used under certain Let conditions fix on both types of fiber (DE-PS 18 11 796).

The same difficulties stand in the way of developing an etching or reserve printing process. Of the The invention was therefore based on the object, white and colored reserves on mixed materials of polyester and To produce cellulose fibers.

This object is achieved according to the invention in that a slightly acidic preparation is applied to the mixed material, at least one etchable reactive dye that stains both types of fiber, or a mixture of at least one etchable reactive dye and at least one disperse dye, the can be converted into a water-soluble anionic form with alkali, and optionally a neutral fixing aid for reactive dyes, then prints a paste containing alkali and a reducing agent, whereupon a fixation with superheated steam or saturated steam in connection with hot air takes place, and if the acidic preparation does not contain the neutral fixing aid, treatment with alkaline Media and a steaming process connects.

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According to this procedure, white reserves are obtained. The alkaline printing paste is used to generate color reserves Vat dyes, alkali-stable or vat disperse dyes or a combination of these Dyes added. According to the invention, conversion articles can also be produced if the acidic Preparation adds non-etchable dyes. These and other preferred embodiments of the invention are described in explained in more detail below.

The substrates colored according to the invention comprise mixed materials made of polyester fibers, in particular polyethylene glycol terephthalate fibers, and natural and regenerated cellulose fibers in all common mixing ratios.

The slightly acidic preparation is expedient by padding or patting, but also by printing applied, especially when large-area patterns (decker) are printed. The embodiment of the Process according to the invention, in which the acidic preparation contains one or more etchable reactive dyes that dye both types of fiber, has the advantage with it that there are no cleavage products of disperse dyes, their elimination from the cellulose fiber Can cause difficulties. These dyes are preferred together with the neutral fixing aid applied for reactive dyes, followed by fixation in a superheated steam atmosphere.

Disperse dyes, which with alkali in a water-soluble Anionic form can be converted, in particular at a higher temperature, are known. The alkali solubility these dyes are caused by functional groups, especially possibly esterified carboxy groups or phenolic or enolic hydroxyl groups or a combination of such groups. In their water soluble

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anionisoheri. Form these disperse dyes are no longer absorbed by the polyester fiber and can easily be removed from the cellulose fiber.

The neutral fixing aid for reactive dyes, 5 to 100 g of which are expediently added per liter of padding liquor or per kilogram of printing paste causes the fixation of the reactive dye on the background already irr. course the steaming operation takes place with superheated steam. at these tools are known to be

Alkali or alkaline earth salts of aliphatic or aromatic, preferably low molecular weight, mono- or polycarboxylic acids, in particular to alkali or alkaline earth salts of multiply halogenated low molecular weight aliphatic carbonyl 5 acids and low molecular weight cyclic carbonic acid esters.

If the acidic preparation is applied in a relatively low-liquid form , for example by spraying on or printing on, then the alkaline etching paste can be printed on without intermediate drying. In general, however, intermediate drying is recommended.

The etching paste contains alkali, preferably in the form of alkali hydroxide or carbonate or a mixture of both as well as a reducing agent common in etching and vat printing inks, preferably a stabilized sulfinate, in particular the sodium salt of hydroxymethanesulfinic acid.

The alkaline

Etching paste added a suitable dye or a mixture of dyes from the series of vat dyes, alkali-stable disperse dyes and vateable disperse dyes are selected. Even Combinations of several dyes from different classes are possible.

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If the alkaline printing paste contains a vat dye, this is followed by a treatment with saturated steam at atmospheric pressure. This will make the vat dye küpt so that it is on the cellulose part of the mixed fiber material can pull up.

Since some of vat dyes are sensitive to temperatures above 100 ⁰ C during the fixing process, however, a high fixing temperature is required for the dyes on the polyester fiber proportion is advisable to add an auxiliary agent above 100 ⁰ C water is split off. This prevents or at least strongly suppresses the otherwise occurring clouding of the color shade. Suitable auxiliaries of this type are aqueous dispersions of polymers, for example ethylene polymers, but especially organic dicarboxylic acids, which are expediently used in the form of their salts, for example their alkali salts. Of these auxiliaries, it is expedient to add 50 to 400 g kilograms of printing paste.

In a further embodiment of the invention, colored reserves are produced with the aid of alkali-stable disperse dyes which are added to the alkaline etching paste will. This alkali-stable disperse dye is advantageous in combination with a vat dye used that matches in color.

In a further preferred embodiment, there are color reserve effects produced with the help of vatting disperse dyes, which are incorporated into the cellulose fiber in vatting form penetrate, where they are firmly anchored in the course of reoxidation.

The fixation of the color depends on the dyes used. As mentioned, when using Vat dyes require saturated steam treatment,

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which can be omitted if, in addition to the reactive dyes, only Disperse dyes are used. When a saturated steam treatment is carried out, the destruction of the reactive dye already takes place in this step the reducing agent and the conversion of the alkali-sensitive disperse dye into its water-soluble one anionic form.

The disperse dyes are appropriately fixed in the same unit as a previous saturated steam treatment with superheated steam or hot air in conjunction with saturated steam. At the same time, the reoxidation of the vat dye is promoted. In case the acidic preparation the neutral fixing aid for reactive dyes contains, the reactive dye is also fixed in this step.

Steaming with superheated steam and hot air fixation are advantageously carried out in an acidic atmosphere, remaining residues of reducing agent that could interfere with the further course of the process, be dismantled. For this purpose, volatile carboxylic acids such as formic acid or Acetic acid, added.

If the acidic preparation does not contain a neutral fixing aid for reactive dyes, it becomes the reactive dye fixed after the fixation of the other dyes by a two-phase steaming process.

For this purpose, alkali is applied to the fiber material, preferably in the form of alkali hydroxide or carbonate, hydrogen carbonate, phosphate or silicate or a mixture of such alkalis. The application can be in any Wise done, for example by spraying, padding or paddling. The subsequent steaming process is advantageously carried out as short-term steaming in saturated steam, which takes 3 to 20 seconds.

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uie usable in the process according to the invention Reactive dyes can be of the various organic Dye classes, for example azo, anthraquinone and phthalocyanine dyes belong to the at least a ß-hydroxyethylsulfonic acid ester group, Vinylsulfonyl group, monochlorotriazine group, dichlorotriazine group, 2,2,3,3-tetrafluorocyclobutane-1-acroylamino group, Vinylsulfonylamino group, ß-hydroxyethylsulfonylaminosulfuric acid ester group, ß-phenyl

'Q contain a sulfonylpropionylamino group or a dichloroquinoxaline residue. Preference is given to the dyes which carry a vinyl sulfone group or which form an intermediate in the reaction.

^ 5 of disperse dyes mixed with alkali in a Can be converted into water-soluble anionic form, preference is given to those whose cleavage products are easy are to be eliminated. Preference is given to dyes which contain one or more carboxylic acid ester groups, and nitro-thiazole dyes.

For the Bun ^ etch reserve effects are suitable on the one hand Disperse dyes with an anthraquinone structure that can be vetted are, and on the other hand naphthalene di- and tetracarboxylic acid derivatives and quinophthalone derivatives, which are resistant to alkali and reducing agents.

The vat dyes are in particular indigoid, thioindigoid, anthraquinoid or naphiochinoid compounds into consideration, which are advantageously used in the commercial dough form.

As a suitable thickener for the padding liquors, which in particular stabilize the fine distribution of the disperse dyes, there are locust bean gum ether thickenings into consideration. Of this, 50 to 200 g of a 4 to 8% strength per liter of liquor are expediently used

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"5-

added to aqueous preparation.

Suitable thickeners for the printing pastes are, for example, mixtures of degraded Gununi varieties and low-viscosity alginates or locust bean gum carboxyethyl ether and starch carboxymethyl ether.

In the following examples, percentages are related on weight. The Color Index numbers were taken from the 2nd edition (1956) and the supplementary volume in 1963.

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example 1

A fabric made of 50% polyethylene glycol terephthalate fibers and 50% regenerated cellulose fibers is made with a liquor padded that in the liter

80 g of the commercially available powder formulation of the reactive dye (which stains both fibers) of the formula

N == N

SO ₂ -CH ₂ CH ₂ -OSO ₃ H

as

100 g of a 5% aqueous solution of a locust bean gum ether , 30 g sodium formate and

Contains 2 g sodium dihydrogen phosphate.

After drying, the fabric is printed with a printing ink of the following composition:

60 g of the commercially available powder formulation of the (alkali-stable) disperse dye of the formula

be with

85 g of the commercial dough setting of the vat dye CI. 73 335 and

115 g of the commercially available dough formulation of the vat dye CI. 73 360 mixed with 030067/0394

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Dilute 10Og of water and pour in

200 g of a mixture in equal parts of the 35% strength aqueous solution of a degraded wheat starch and entered the 10% aqueous solution of a low viscosity sodium alginate.

Then will
100 g glycerine,
100 g sodium carbonate,

30 g of 32.5% sodium hydroxide solution and
100 g of sodium formaldehyde sulfoxylate were added.

With

110 g of water or the aforementioned thickening is made up to 1000 g.

After printing and drying, the goods are treated with superheated steam for 8 minutes at 180 ^° C., rinsed briefly, reoxidized at 50 ^° C. with 2 g / l hydrogen peroxide and 5 ml / l acetic acid, rinsed again and finally with 0.5 g / l washed a 20-fold oxyethylated nonylphenol at 90 ⁰ C, rinsed and cetrocknet.

A brilliant red print on a greenish yellow ground with good fastness properties is obtained.

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Example 2

A fabric made of 65% polyethylene glycol terephthalate fibers and 35% cotton is treated with an analogous to Example 1 composite fleet padded that

70 g of the commercially available powder formulation of the reactive dye of the formula

HO ₃ SO-CH ₂ CH ₂ -SO ₂

COOH

and

40 g of the commercially available liquid formulation of the (alkali-sensitive) Disperse dye of the formula

contains.

After padding and drying, the goods are printed with a printing ink that, apart from the dye, is the same Ingredients such as the printing ink described in Example 1 and beyond

Contains 200 g of the disodium salt of maleic acid. The following dyes are added to the printing ink:

12 g of the commercially available liquid formulation of the (vettable) disperse dye of the formula

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-Ί3 -

(NH ₂ ) OH O OH

(OH) NH ₂ 0 NH-CH ₂ -OH

15 g of the commercially available dough formulation of the vat dye CI. 69 800 and

120 g of the commercially available dough formulation of the vat dye CI. 73 360.

After printing and drying, the goods are ^{steamed for 10 minutes at 102 °} C. in saturated steam and then for 7 minutes at 175 ^° C. in superheated steam. The further treatment is carried out as in the example

The result is a red-violet print on a reddish-yellow background with good fastness properties.

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Example 3

A knitted fabric made from 50% polyethylene glycol terephthalate fibers and 50% highly wet-strength regenerated cellulose fibers are padded with a liquor that is per liter

50 g of the commercially available liquid formulation of the (alkali-sensitive) Disperse dye of the formula

" ₃

H ^ CO-CO- / V-N == N- / \

CH ₃ CO-NH CH ₂ CH ₂ COOCH ₃

and

50 g of the commercially available powder formulation of the reactive dye of the formula

OCH ₃

/ - H (T ^

H ₃ CO

/ ^h 3 H0 _o S0-CH "CH" - S0 "-f ^ V- Ν_Ν-η ^

Λ ^ -

SO-H ³

as

g of a 5% aqueous solution of a locust bean gum ether,
Contains 50 g of ethylene carbonate and 2 g of sodium dihydrogen phosphate .

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After drying, the knitted fabric is coated with a printing ink of the same composition as in Example 1, but with

150 g of the commercial dough setting of the vat dye es CI. 73 360, printed (which also includes the Polyester fiber content).

After printing and drying, the fabric is in a pad bath with a squeeze effect of 70% 50 g / l acetic acid padded and then steamed for 8 minutes at 175 ° C in superheated steam. The further treatment takes place as in example 1.

A pink print on a golden yellow ground with good fastness properties is obtained.

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Example 4

A fabric made of 70% polyethylene glycol terephthalate fibers and 30% cotton is padded as in Example 1 with a liquor that is in the liter

50 g of the commercially available liquid formulation of the (alkali-sensitive) disperse dye of the formula

H ₂ CH ₂ CN

and

50 g of the commercially available powder formulation of the reactive dye of the formula

CH,

= CH-SO ₂ -

^ COOH

SO ₃ H

as well as the other ingredients mentioned in Example 1 contains.

After drying, the fabric is printed with a printing ink that contains the same additives as in Example 2, but as dye components

50 g of the commercially available liquid formulation of the {alkali-stable) disperse dye of the formula

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O OH

N-CH ₂ -CH-CH ₃

20 g of the commercially available liquid formulation of the (vettable) disperse dye of the formula

(NH ₂ ) OH 0 QH

and

(OH) NH ₂ O NH-CH ₂ OH

25 g of the commercially available dough formulation of the vat dye CI. 69,800 were added.

20 The further treatment is carried out as in Example '. 2

The result is a rich green print on an orange background with good fastness properties.

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Example 5

The same fabric as in Example 4 is padded with a liquor as there, in addition to those described there Additives

50 g of the commercially available liquid formulation of the alkali-sensitive) Disperse dye of the formula

CH ₀ CH ₀ COOCH-

²

^> = ^/ J '^ CH ₂ CH ₂ COOCH ₃

CH ₃ CO-NH

and

50 g of the commercially available powder formulation of the reactive dye the formula

SO ₃ H HO ₃ S

contains.

The padded and dried fabric is coated with a printing ink of the same composition as in Example 2 » but the following dye components, printed:

60 g of the commercially available liquid formulation of the (viable) disperse dye of the formula

(NH ₂ ) OH 0 OH

(OH) NH ₂ 0 NH-CH ₂ OH and

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75 g of the commercially available dough formulation of the vat dye CI. 69 800.

The further treatment takes place as in example 2.

The result is a deep blue print on a red background with good fastness properties.

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Example 6

Asern a fabric of 50% Polyäthylenglykolterephthalatf and 50% regenerated cellulose fibers is padded with a liquor containing per liter

5 50 g of the commercially available liquid formulation of the (alkali-sensitive) disperse dye of the formula

CN Λ CH ₂ CH ₂ CO-OCH ₂ CH ₂ Oh

O ₂ N- / \ - N ^N ~ \ / X

1 0 '*'' ^ PH PH PP

and

50 g of the commercially available powder formulation of the reactive dye of the formula

CH ₃ CO-

as

100 g of the thickening described in Example 1

and

Contains 2 g sodium dihydrogen phosphate ₂₅ .

After drying, the fabric is printed with a printing ink which, apart from the dye, has the same components as described in Example 1 contains. 30th

As a dye component are the printing ink

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2A

60 g of the commercially available powder formulation of the (alkali-stable) disperse dye of the formula

admitted.

The printed and dried goods are steamed for 7 minutes at 180 ⁰ C in superheated steam, padded with a squeeze effect of 70% with a liquor of 100 g / l 32.5% sodium hydroxide solution and 150 g / l sodium carbonate and 8 seconds in saturated steam 102 ⁰ C attenuated. The completion takes place as in example 1.

The result is an orange-colored print on a bluish- red background with good fastness properties.

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Example 7

A fabric of 65 I Polyäthylenglykolterephthalatfasern and 35% cotton is padded as in Example 1 with a liquor which, in addition to those described there aids

90 g of the commercially available powder formulation of the alkali-sensitive) Disperse dye of the formula

CH ₂ CH ₂ OH

10g of the commercially available powder setting of the Reactive dye of the formula

SO ₂ -CH ₂ CH ₂ -OSO ₃ H

and

50 g of the commercially available powder formulation of the reactive dye CI. 20th were admitted.

The padded and dried fabric is printed with a printing ink that 70 g of the commercially available liquid formulation of the (alkali-stable) disperse dye of the formula

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OH

J-CH ₂ -CH-CH ₃

and the other printing paste additives described in Example 1 contains.

The printed and dried fabric is passed ^{through superheated steam at 180 °} C. for 7 minutes and then treated further as in Example 1.

The result is a greenish-yellow print on navy blue Fond with good fastness properties.

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Example 8

A fabric made of 65% polyethylene glycol terephthalate fibers and 35% cotton is printed with a printing paste that has the following composition:

90 g of the commercially available powder formulation of the alkali-sensitive disperse dye of the formula

CH ₂ CH ₂ OH

20 g of the commercially available liquid formulation of the alkali-sensitive) disperse dye of the formula

and 80 g of the commercially available powder formulation of the

Reactive dye CI. 20 505 and 400 g of a 5% aqueous solution of a Johannis-

Bread Gum Essences, 30 g sodium formate,

2 g sodium dihydrogen phosphate and 378 g water 1000 g.

After drying, the fabric is printed with a printing ink which is composed according to Example 1, but does not contain glycerol and 150 g of sodium formaldehyde sulfoxylate and correspondingly 160 g of water or thickener. After printing and drying, the product is treated for 8 minutes at 18O ⁰ C with superheated steam,

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briefly rinsed as usual reoxidized with 0.5 g / l of a 2Ofach oxyethylated nonylphenol at 90 ⁰ C, rinsed and dried.

A brilliant red-black print sample with good fastness properties is obtained.

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ORIGINAL INSPECTED

Claims (8)

HOE 79 / F 207 PATENT CLAIMS 1. Process for producing reserve effects Mixed materials of polyester and cellulose fibers, characterized in that one is applied to the material application of a weakly acidic preparation which contains at least one reactive dye which can be etched dyes both types of fiber, or a mixture of at least one etchable reactive dye and at least one disperse dye that reacts with alkali can be converted into a water-soluble anionic form, and optionally a neutral fixing aid for reactive dyes contains, subsequently prints a paste containing alkali and a reducing agent, followed by fixation with superheated steam or saturated steam in conjunction with hot air, and if the acidic preparation is not the neutral one Contains fixing agent, followed by an alkaline treatment and a steaming process. 2. The method according to claim 1, characterized in that an alkaline paste is printed which contains at least one vat dye, followed by said before Fixing step a treatment with saturated steam takes place. 3. The method according to claim 2, characterized in that the printing paste contains a tool that cleaves the above 100 ⁰ C water. 4. The method according to claim 1 to 3, characterized in that the alkaline printing paste contains at least one alkali-stable disperse dye. 030067/0394 ORIGINAL INSPECTED HOE 79 / f 207 5. The method according to claim 1 to 4, characterized in that the alkaline printing paste at least Contains a viatable disperse dye. 6. The method according to claim 1 to 5, characterized in that the acidic preparation is at least one non-etchable Contains dye. 7. The method according to claim 1 to 6, characterized in that steamed with an acid-containing steam will. 8. The method according to claim 1 to 7, characterized in that the impregnated with the acidic preparation Material is dried with the alkaline paste before printing. 030067/0394