DE3444283A1 - AGENT FOR THE PRODUCTION OF WHITE AND COLORED PUTS ON SYNTHETIC HYDROPHOBIC FIBER MATERIAL - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT HOE 84 / F 287 Dr.CZ/sch

Means for producing white and colored etching on synthetic hydrophobic fiber material

The present invention is concerned with the production of discharge printing patterns on finished colored polyester materials.

It is known that real dyeings on hydrophobic polyester textile fibers are produced by dissolving colored organophilic substances generated in the plastic fiber mass. In practice, this dissolving process can be achieved by increasing the temperature up to Glass transition temperature can be made. But with such a way of working, the flexibility suffers the goods and their value as clothing textile material. For this reason, the dissolving process is carried out in the presence of a so-called "Carrier" at low temperatures.

Carriers are those organic substances which, when the fibers swell, cause the colored substances to dissolve accelerate or promote into the fiber mass. State-of-the-art technology is used in textile printing This dissolution process of the colored substances in the hydrophobic fiber mass at temperatures between 160 and 180 ° C in Presence of superheated steam made under the designation HT steam fixation. The coloring can also be carried out according to the exhaustion method in the dye bath.

Genuine discharge printing articles made of fine polyester textile material are not yet known because they are located inside the fiber colored substances cannot be destroyed with neutral aqueous discharge printing pastes. Saponify alkaline printing pastes on the other hand the fine polyester material.

In order to achieve etch-like effects, one therefore works with reserves in practice. Reserves are made before the basic coloring Applied in print samples on the goods. About costs

'- ·' · 3U4283 C

To save, the jobs are preferably carried out wet on wet in an overlapping manner. To get a good sharpness of the contours To obtain, both the printing pastes for the reserves and the patting or printing pastes for the Basic color can be set stiff. As a result, the print through on the goods also suffers with the result that the Color effects can only be seen on one side. According to this working method, there are parbe effects on the same side with sharp ones Not producing contours.

It has now been found that you can easily match Can produce discharge printing patterns on pre-fixed basic colors on hydrophobic polyester textile materials, if a mixture according to the invention of the following components is used as the etchant:

(A) a hydrazine derivative of aryl or aralkyl carboxylic acids or sulfonic acids or salts thereof, preferably those in their free acid form and at the same time free base form of the general formula

(X) _n

NH-NH ₂

correspond, in which η is a number from 1 to 3 and X is a group of the formula

Represents -COOH, -CH ₂ -COOH, -SO ₃ H or CH ₂ -SO ₃ H,

where multiple X is identical or different, and in which the aromatic ring system is optionally contain fused-on further rings and / or by non-ionic radicals, preferably halogen atoms, alkyl, Alkoxy and nitro groups, may be substituted;

(b) a polyalkylene glycol, preferably polyethylene glycols corresponding to the general formula

OH - (CH ₂ - CH ₂ - O) _n H
5

wherein m is a number from 2 to 100 ";

(c) a nitrogen compound according to the general formula

Y _a N (R) _b

where a is not equal to b and each of which is zero or one
Represents a number from 1 to 3 - provided that the sum of a + b is always 3 - and in which Y is a hydrogen atom or an alkyl group with 1 to 6, preferably 1 to 4, carbon atoms, where multiple Y is the same or is different, and R is
Hydrogen atom or a hydroxyalkyl group with 1 to 6, preferably 1 to 4, carbon atoms in particular

-C ₂ H ^ OH, C ₅ HgOH or C ₄ HgOH, where multiple R is the same or different;

(d) a hydrophilic solvent of the formula
R 0 (CH ₂ - CH ₂ - O) _n H

where R = H or an alkyl group with 1 to 4 carbon atoms and η = 0 or a number from 1 to 3
mean;
30th

(e) an anionic emulsifier and

(f) a copolymer mixture of water-insoluble carboxyl groups Polyvinyl acetate, which is produced by copolymerization of polyvinyl acetate with aliphatic un-

saturated carboxylic acids with 1 to 6, preferably 2 to 4 carbon atoms in the aliphatic radical, preferably methacrylic acid, acrylic acid or crotonic acid is, and in water-insoluble crosslinked carboxyl-containing Polyacrylic acid ester obtained by copolymerization in an aqueous emulsion in the presence of anionic Emulsifiers made from acrylic esters such as ethyl, methyl, propyl or butyl acrylate, and aliphatic unsaturated mono- or dicarboxylic acids with 1 to 6, preferably 2 to 4 C atoms in the aliphatic radical, preferably acrylic acid, methacrylic acid or maleic acid, is synthesized.

With a printing paste containing 500 g of the invention per kilogram Contains etching agent, you can create contour-true etching print patterns on finished colored polyester goods, if the coloring is done with an etchable disperse dye.

The present invention also relates to pressure etchants to carry out the claimed process, characterized by a content of a mixture of components (a), (b), (c), (d), (e) and (f).

The mixture component (a) in the etchant according to the invention is, for example, 2-, 3- or 4-hydrazino-benzenecarboxylic acid; 2-hydrazino-phenylacetic acid, hydrazino-naphthalene-carboxylic acids; 2-, 3- or 4-hydrazino-benzene-sulfonic acid- (5); 4-, 5- or 8-hydrazinonaphthalene-sulfonic acid- (i); 1- or 6-hydrazino-naphthalenesulfonic acid- (2); 4-hydrazino-toluene-sulfonic acid- (2); 2- or 3-hydrazino-benzene-disulphonic acid (1,4) and 4-hydrazinobenzene-disulphonic acid (1,3) and corresponding alkali metal or ammonium salts on the acid residue or salts of hydrohalic acids on the hydrazino group. The mixture component (a) is used in amounts between 5 and 60 g, preferably between 15 and 40 g per kilogram of the etching

printing paste used. This crowd is mainly directed according to the intended color depth of the fund.

Polyethylene glycols are primarily used as polyalkylene glycols corresponding to component (b) for the etchant according to the invention expediently with an average molecular weight between 300 and 2000 in question. The amount the mixture component (b) required in the discharge printing paste ranges between 30 and 300 g, preferably between 60 and 200 g per kilogram of discharge printing paste.

The mixture component (c), especially N, N-dimethyl-N-ethanol-amine or ammonia, serves to neutralize compound (a) and the copolymer mixture (f); Therefore the amount of (c) used depends mainly on the amount of the mixture components (a) and (f) present in each case.

The mixture component (d), particularly lower aliphatic Alcohols such as methanol or ethanol or their etherification products with ethylene glycol such as ethylene glycol monoethyl, Monobutyl or monomethyl ether is used to dissolve the water-insoluble copolymer mixture (f). It comes in amounts between 1 - 10 g, preferably between 3 and 5 S per Kilograms of discharge printing paste for application.

As anionic emulsifier (s) for the discharge printing paste according to the invention For example, ammonium lauryl sulfate or sodium ß-hydroxyoctadecane sulfonate are suitable. 30th

However, this emulsifier component is also used during manufacture the copolymer mixture (f) is used, which means that there is usually no additional addition.

The copolymer mixture Cf) consists of two copolymers, those in the aqueous dilutions of the mixture component

AO

(d) exhibit opposite dissolution behavior at the neutral point. The vinyl acetate copolymer is according to DE-PS 803 956 or GB-PS 733 507 manufactured. This copolymer can be dissolved in a 50% aqueous ammoniacal Dissolve methanol well at pH values above 7.5. At pH values below 6 it becomes insoluble and separates as viscous mass from the solution. According to the invention, 1 kilogram of discharge printing paste contains 3 to 50 g, preferably between and 20 g of this copolymer.

The other copolymer is made, for example, from ethyl acrylate, methacrylic acid, according to F-PS 12 80 792, Example 6 and glyoxyl-tetra-alkyl acetate in the presence of an anionic one Emulsifier produced as an aqueous emulsion.

This copolymer shows no thickening effect in aqueous media at pH values below 6.0. Above pH 6.5 the copolymer becomes increasingly viscous in alkaline-aqueous media with increasing pH. As alkali is ammonia used according to the invention. 1 kg of the invention Discharge printing paste contains 30 to 150 g, preferably up to 100 g, of this copolymer.

With regard to the preparation of the discharge printing pastes, it has proven to be rational if components (b) to

(f) as a finished mixture and component (a) as an individual component in aqueous Ν, Ν-dimethyl-N-ethanol-amine-containing Solution of the discharge printing paste admixed.

The pH of the aqueous solution of the neutralized mixture components (a) and (f) should expediently be im Range between 6.5 and 8.8.

According to the invention, textile fabrics, in particular woven or knitted fabrics, made from synthetic fibers with a hydrophobic character are used all by heat-fixable dyes, in particular Disperse dyes, dyeable materials in

34U283

Question, especially made of fibers of linear aromatic polyesters such as polyethylene terephthalate, also made from cellulose triacetate, cellulose 2 1/2 acetate and polyamide fibers. as well Textile goods based on mixtures of these synthetic fibers with fibers of natural origin can be used other synthetic fibers.

Pur the production of pond colors and colored effects The process of the present invention comes from the class of disperse dyes under this term known compounds suitable for application to the synthetic fibers referred to above are used, for example those included in the Color Index 3 · Edition 1971 and supplements 1975 under the generic name "Disperse Dyes "will be listed.

The selection of the etchable dyes for the claimed process can be based on the mild effect of the etchant can only be taken experimentally. The range of disperse dyes, which can be etched in accordance with the present invention is sufficient and extends from yellow to blue.

In terms of printing technology, to produce the etching effects in accordance with the method, the procedure can be that the textile fabric is removed or knitted fabrics first padding with a dye liquor containing etchable disperse dyes, then drying, fixed and completed by a reductive alkaline treatment, washing and drying. The fixation creates thus a solution of the dye in the hydrophobic fiber.

An advantage of the method according to the invention is, for example to mention the possibility of unlimited storage of the basic colors.

With a time lag, the basic colors can then be printed with etching patterns in line with the market.

Pie fixation of Ätzmuste can, as usual, in hot air or superheated steam at temperatures between 160 ⁰ C and 220 ⁰ C for 45 seconds to 8 minutes or in the steam pressure of 1.2 to
1.4 atm for 10 to 50 minutes, preferably 15 to 20
Minutes. The completion of the fixed prints requires after rinsing with water, as usual, a reductive aftertreatment as well as a final rinsing and drying again.

example 1

a) A fabric made of polyester fibers is made with a liquor

40 g of the dye CI. Disperse Violet 48
938 g of water
20 g acetic acid (30 #ig) and

2 g of wetting agent
1000 g

padded at room temperature, dried and 20 minutes
Fixed in the pressure damper at 1.5 atm.

The dyed fabric is then rinsed with water and, as usual, followed by a reductive aftertreatment Subjected to rinsing and drying.

b) fabric of the same fiber type as in example 1a)
with a dye liquor

60 g of CI. Disperse Red 160
10 g citric acid (30 #ig)

2 g wetting agent and
928 g of water
1000 g

padded, dried and at 1.5 atmospheres in pressure steam

fixed for 20 minutes. After that, the fabric will be like in example 1a) completed.

c) To prepare the etching paste, two stock solutions are first prepared:

I 33 g of 4-hydrazino-benzene-1-sulfonic acid 5 49.4 g water

17.6 g Ν, Ν-dimethylaminoethanol and 100 g stock solution I with a pH of 7.5

II In 40 g of a 50% strength aqueous methanol solution and 10 10 g of 25 % aqueous ammonia are added with stirring

in portions
50 g of the copolymer of vinyl acetate and

Crotonic acid dissolved at room temperature. Then add to the solution in be-15 written order

1403 g of polyethylene glycol with a MW of 400 1700 g of the 35 $ strength aqueous copolymer mixture

Sion from glyoxyl-tetra-alkylacetal, acrylic acid ethyl ester and methacrylic acid 20 2g ammonium lauryl sulfate emulsifier and

50 g Ν, Ν-dimethylaminoethanol 3255 g with a pH of 6.8

d) The dyed fabrics from Examples la) and Ib) wer-25 the one with the following discharge printing pastes

Printing paste 1: 100 g of the stock solution I from Example Ic)

400 g of the stock solution II from Example Ic)

22 g Ν, Ν-dimethylaminoethanol 30 300 g of a 10% aqueous kernel meal

ether solution

X g of water as compensation 1000 g

Printing paste 2: 100 g of the stock solution I from Example 1c)

400 g of the stock solution II from Example 1c) 22 g of Ν, Ν-dimethylaminoethanol 60 g of the dye CI. Disperse Yellow 198

300 g of a 10bigen aqueous kernel meal

ether solution

X g of water as compensation 1000 g
10

printed in punctiform patterns, dried and then treated ^{in a high-temperature steamer at 180 °} C. for 7 minutes to etch or fix the applied dyes. The goods are then rinsed with water, after-treated reductively in an aqueous liquor with sodium hydroxide solution, sodium dithionite and a nonionic surfactant, rinsed again with water and finally dried.

After completion of the etching prints one receives on the goods from Example 1a) yellow and white point-like patterns violet background and on the goods from example 1b) yellow and white punctiform patterns on a red background.

Claims (2)

- '~ Φ - HOE 84 / P 287 1. Means for producing white and colored etching on textile Polyester material, characterized in that it consists of a mixture of (A) a hydrazine derivative of aryl or aralkyl carboxylic acids or sulfonic acids or salts thereof, (b) a polyalkylene glycol, (c) a nitrogen compound of the general formula where a is not equal to b and each of which is zero or a number from 1 to 3 - with the proviso that the sum of a + b is always 3 - and in which Y is a hydrogen atom or an alkyl group with 1 to 6, preferably 1 to 4 C atoms, where multiple Y is identical or different and R is a hydrogen atom or a hydroxyalkyl group with 1 to 6, preferably 1 to C atoms, in particular -C ₂ H ^ OH, C ^ HgOH or C.HgOH, where multiple R is the same or different,
(d) a hydrophilic solvent of the formula R 0 (CH ₂ - CH ₂ - O) _n H where R = H or an alkyl group with 1 to 4 carbon atoms and η = 0 or a number from 1 to 3,
(e) an anionic emulsifier and (F) a copolymer mixture of water-insoluble carboxyl-containing polyvinyl acetate that by Copolymerization of polyvinyl acetate with aliphatic unsaturated carboxylic acids with 1 to 6, above - Vi - HOE 84 / P 28-7 ' preferably 2 to 4 carbon atoms in the aliphatic radical, is produced, and crosslinked insoluble in water carboxyl group-containing polyacrylic acid ester, which by copolymerization in an aqueous emulsion in Presence of anionic emulsifiers from acrylic acid esters and aliphatic unsaturated mono- or Dicarboxylic acids with 1 to 6, preferably 2 to 4 carbon atoms in the aliphatic radical, is synthesized. 2. Means according to claim 2, characterized in that the mixture component (a) is a hydrazine derivative of the general formula w w is, where η is a number from 1 to 3 and X is a group of the formula -COOH, -CH ₂ COOH, -SO ₅ H or -CH ₂ SO ₃ H, where multiple X is the same or different and in which the aromatic ring system is optionally may contain fused-on further rings and / or be substituted by non-ionic radicals. 3 · Agent according to claim 1, characterized in that the mixture component (b) is a polyethylene glycol of the general formula OH - (CH ₂ - CH ₂ - 0) _{m is} H, JO where m is a number from 2 to 100. 4 · Means according to claim 1, characterized in that the Mixture component (a) 4-hydrazinobenzene-1-sulfonic acid is. 5 ' Process for the production of white and colored etchings on synthetic hydrophobic fiber material, thereby identified - HOE 8'4 / F 28-7 " draws that a mixture of the following components is used as the etchant: (a) a hydrazine derivative of aryl or aralkyl carboxylic acids or sulfonic acids or salts thereof, (b) a polyalkylene glycol, (c) a nitrogen compound of the general formula where a is not equal to b and each of which is zero or a number from 1 to 3 - with the proviso that the sum of a + b is always 3 - and in which Y is a hydrogen atom or an alkyl group with 1 to 6, preferably 1 to 4 C atoms, where multiple Y is identical or different and R is a hydrogen atom or a hydroxyalkyl group with 1 to 6, preferably 1 to C atoms, in particular -C ₂ H ^ OH, C ^ HgOH or C.HgOH, where multiple R is the same or different, (d) a hydrophilic solvent of formula 20 R - _{O (CH 2} - CH ₂ - O) _n H where R = H or an alkyl group with 1 to 4 carbon atoms and η = 0 or a number from 1 to 3 mean (e) an anionic emulsifier and (f) a copolymer blend of water-insoluble polyvinyl acetate containing carboxyl groups, which is produced by copolymerization of polyvinyl acetate with aliphatic unsaturated carboxylic acids with 1 to 6, preferably 2 to 4 carbon atoms in the aliphatic radical, is prepared, and in water-insoluble crosslinked carboxyl-containing polyacrylic acid ester, the by copolymerization in aqueous emulsion in J5 Presence of anionic emulsifiers from acrylic acid 3A44283 HOE 84 / P 287 esters and aliphatic unsaturated. Mono- or dicarboxylic acids with 1 to 6, preferably 2 to 4 C atoms in the aliphatic radical, is synthesized.