DE3903666A1 - Process for dyeing and printing blends of polyester with natural fibre materials - Google Patents

Abstract

The invention relates to a process for dyeing and printing blends of polyester with natural fibre materials, which is characterised in that the dyebaths, tanning liquors or print pastes contain one or more compounds of the general formula I <IMAGE> .

Description

When dyeing and printing polyester-cellulose or Polyester-wool blends are usually the polyester content of the mixed fabric with disperse dyes and the cellulose or wool content with reactive, direct, Developmental, leuco vat nests, vat, sulfur vat or sulfur dyes dyed or printed.

The proportion of disperse dye causes difficulties, not when dyeing the polyester portion completely on this, but on the cellulose or wool fiber remains and soils what adversely affect the brilliance of the coloring and its fastness affects. The dye remaining there has one different, cloudy shade than that dissolved in the polyester fiber. This is particularly the case with bright or brilliant Coloring noticeably noticeable. Because of its insufficient Affinity for cellulose or wool fiber deteriorated he also the wet, rub and light fastness the coloring. This manifests itself e.g. B. in subsequent Washing processes, e.g. B. the household laundry of the consumer, by repeatedly bleeding out disperse dye and stains other colored or even white accompanying fabrics. This is a particular problem with deep stains, too the achievement of which excess dye is used, for dyeings in which the cellulose or wool content should remain uncolored or in prints where it is different colors printed or printed and unprinted Places there.  

Another difficulty in dyeing or printing on such mixed materials stems from the dispersants forth, with the help of the disperse dyes or the dye preparations, some of which are disperse dyes included, manufactured. This preferred anionic dispersants are depending on their Manufacture light brown to black products, the one Have affinity for cellulose or wool and feel light deposit there and again especially in bright and brilliant colors cause tarnishing.

One works this problem i. a. by washing the color counter, in which the soiling particles from Tissues are removed. This washing process is time - and expensive. Since washing the dye at temperatures performed near the dyeing temperature disperse dye that has entered the wash liquor soiling the polyester part irreversibly. If the post-cleaning is carried out reductively or oxidatively or is the coloring of the cellulose part in reductive environment, becomes the soiling disperse dye destroyed, and fission products can arise, which in turn get soiled again.

To avoid these difficulties, the patent literature the use of ionic or else non-ionic polymeric auxiliaries used in dyeing or can be used for post-washing and Z. B. in OS 34 46 922, DP 34 14 306, JP 47-39309, JP 49-117782, JP 49-117783 or JP 51-119886.

It has now surprisingly been found that the soiling the cellulose or wool content through disperse dye preparations when dyeing or printing  of polyester-cellulose or polyester-wool blended fabrics is prevented or suppressed to a high degree, if when dyeing and printing the blended fabrics Dye baths, padding liquors or printing pastes one or more Contain compounds of general formula I.

The present invention thus relates to a method for dyeing and printing mixed fabrics made of polyester and natural fiber materials, characterized in that is that in the dye baths, padding liquors or Printing pastes one or more connections of the general formula I.

are included in what
R and R ′ independently of one another are hydrogen, linear or branched alkyl having 1 to 18 carbon atoms, which is optionally substituted by chlorine, bromine or alkoxy having 1 to 4 carbon atoms; Cyclopentyl; Cyclohexyl; Allyl; Methallyl; Acrylic; Methacrylic; Crotyl; Phenyl which is mono- or disubstituted by chlorine, bromine, methyl, alkoxy having 1 to 4 carbon atoms,

wherein x ⁵ is a number from 1 to 10; Benzyl or COR ", where R" can have one of the meanings of R, but is independent of it,
D¹ to D⁵ linear (C₂-C₁₀) - or cyclic (C₃-C₁₀) - alkylene units which are unsubstituted or by (C₁-C₄) alkyl, (C₁-C₄) alkoxy or

wherein p stands for a number from 0-10, are substituted, or

in which D⁶ has the same meanings as these independently of D¹ to D⁵ and x ⁶ is a number from 1 to 100, where all groups D¹ to D⁵ can be interchanged as desired within an idealized molecule of general formula I and thus a statistical distribution subject to
X ¹ to X ⁵ independently of one another are a number from 1 to 100,

means
R¹ 1.4-phenylene, 1.2-phenylene, 1.3-phenylene, 1.4-naphthylene, 1.8-naphthylene, 2.2'-, 2.4'- or 4.4'-biphenylene, linear or branched alkylene with 2 to 18 carbon atoms or cyclic alkylene with 4 to 6 carbon atoms, where all R¹ may be optionally substituted by at least one group SO₃M or COOM, where M is hydrogen, a cation from the series of alkali metals or a cation from the series of ammonia, primary, secondary, tertiary or quaternary amine; or by

where the last residue is substituted by two residues R 1 at the same time, and w is a number from 1 to 5, where the residues R 1 are subject to a statistical distribution and
y 1 and y 2, independently of one another, mean a number from 0 to 20, provided that the sum y 1 + y 2 is 0 to 20.

In the general formula I, those for R, R ′ and R ′ ′ standing linear or branched, optionally substituted Alkyl groups with 1 to 18 carbon atoms for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl, pentyl-3, n-hexyl, 2-ethylbutyl, n-heptyl, i-heptyl, octyl-2, 2-ethylhexyl, i-nonyl, n-decyl, i-decyl, n-dodecyl, n-hexadecyl, n-octadecyl or else Mixtures (C₄-C₉) - or (C₈-C₉) alkyl, (C₆-C₁₀) - or (C₈-C₁₀) alkyl, (C₁₀-C₁₂) alkyl, (C₁₂-C₁₄) alkyl, (C₁₂-C₁₈) alkyl, (C₁₃-C₁₈) alkyl or (C₁₄-C₁₈) alkyl.

Correspondingly substituted radicals are, for example 2-chloroethyl, 3-chloropropyl, 1-chloropropyl-2, 2-bromoethyl or 3-methoxybutyl.

R, R ′ and R ″ are preferably hydrogen and alkyl radicals with 1 to 8 carbon atoms, particularly preferred Hydrogen and methyl.

D¹ and D⁶ are preferably ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexamethylene, 3-methoxy-1,2-propylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1.2 and 1.4 demethylene cyclohexane.

D¹ and D⁶ are particularly preferably ethylene, 1,2-propylene and 1,4-butylene.  

Preferred values for x ¹ and x ³ to x ⁶ are 1 to 80. Preferred values for x ² are 1 to 4.

R¹ is linear or branched alkylene with 2 up to 18 carbon atoms is, for example, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, sec-butylene, tert-butylene, n-pentylene, 3-methylbutylene, n-hexylene, 2-ethylbutylene, n-heptylene, i-heptylene, octylene, 2-ethylhexylene, i-nonylene, n-decylene, i-decylene, n-dodecylene, n-hexadecylene, n-octadecylene or mixtures (C₄-C₉) - or (C₈-C₉) alkylene, (C₆-C₁₀) - or (C₈-C₁₀) - Alkylene, (C₁₀-C₁₂) alkylene, (C₁₂-C₁₄) alkylene, (C₁₂-C₁₈) - Alkylene, (C₁₃-C₁₈) alkylene or (C₁₄-C₁₈) alkylene.

R 1 is preferably the aromatic radicals, particularly preferably 1,4-phenylene, 1,3-phenylene and 1,2-phenylene.

Preferred values for y 1 and y 2 are 1 to 10.

The compounds of the general to be used according to the invention Formula I correspond to the prior art producible as he z. B. from US 34 16 952, US 44 63 165, US 47 36 014 or US 6 84 511 emerges.

The polyester portion of the polyester cellulose or polyester Wool blended fabrics can be mixed with disperse dyes according to the so-called pull-out process under HT conditions or at cooking temperature with carrier additive, the cellulose or wool portion of the blended fabrics can be reactive, direct, Developmental, vat, leuco vat nests, sulfur vat and Sulfur or with reactive and direct dyes from aqueous Fleet to be colored. The dyes can, however also according to the so-called continuous process by impregnation of the fabric with an aqueous padding liquor, the contains these dyes and then fixing these dyes the fiber by thermal insulation, steaming or a  so-called air passage can be applied to the fiber. In principle, it is possible to use the dyes for the Polyester content and for the cellulose or wool content to pad together or separately.

A separate padding liquor can be used during dyeing on the fabric chemicals such. B. alkali and Reducing agents are applied. Through a chemical The alkali fixes the reactive dye on the reaction Cellulose or wool fiber that converts reducing agents the vat or sulfur vat dye in a cellulose fiber affine form.

When printing on the mixed fabric, the is by means of Printing paste on the disperse dye applied to the fabric in the polyester fiber by HT steam, pressure steam or dry heat fixed.

In principle it is possible to change the polyester content and then to dye the cellulose or wool content. It However, the cellulose or Wool portion and only then the polyester portion dyed will.

There are also dyeing processes in which one or is dyed in two baths or in one or two stages. Detailed Information on the details can be found e.g. B. in Melliand Textile Reports 61, 261 (1980); Melliand textile reports 64, 290, 357 (1983) and man-made fibers / textile industry 1974, 756.

The amounts of compounds of general formula I that the dyeing pad liquors by the process according to the invention added, naturally depend on the Soiling tendency of the disperse dye preparations used,  according to the dye content in the Dye liquor or printing paste, after the squeezing effect and according to the proportion of cellulose or wool in the blended fabric. When disperse dye preparations from strong soiling dyes and also strong soiling dispersants are used if high amounts of dye are used when picking up the liquor is high and if the cellulose or wool content of the blended fabric with the same amount of disperse dye used increases, larger amounts of the connections must be made of the general formula I can be used.

As a rule, the amounts of compounds fluctuate general formula I in the padding fleet between 0.1 and 50 g / l, preferably between 1 to 20 g / l. Especially 1 to 10 g / l are preferably used.

When dyeing from an aqueous dye liquor, the Amount also according to the tendency of the disperse dye to become dirty and its dispersants, after which Dye concentration in the dyeing liquor, i.e. after Pure dye content of the disperse dye used and according to the fleet ratio and the Cellulose or wool content of the blended fabric.

Here, as a rule, based on the used Pure dye amount, 1 to 1000%, preferably 10 to 500%. 10 is particularly preferably used until 100%.

The amounts used in the chemical log fleets will fluctuate within the same limits as for the Dyeing pad fleets. If the disperse dyes used by the reducing agent or the alkali Chemical log fleet can be easily destroyed and that  Fission products show a low tendency to soiling, can the amounts of compounds of the general. Formula I can be reduced accordingly.

The compounds of general formula I are according to the invention Procedures usually as more manageable aqueous solutions are used and are in the Fleets and baths stirred in well.

According to the inventive method, the Compounds of the general formula I the chemical pad fleets and particularly preferably the colorant Dye baths or printing pastes added. With the latter use in padding fleets is again preferred.

The method according to the invention shows advantages in particular when dyeing polyester-cellulose blended fabrics.

The cellulose portion with sulfur or Vat dyes, but especially with reactive dyes, colored. A particularly preferred method is the one in which the polyester content in the so-called Thermosol process and the cellulose part with reactive dye is colored, in particular the Polyester portion colors first.

To clarify the inventive concept are below some staining examples listed.

Example 1

30 g of a commercially available, approximately 25% pure dye-containing liquid formulation of CI Disperse Blue 165 and 10 g of a 40% aqueous solution of the compound of general formula I in which R and R 'are hydrogen, D¹, D² and D⁴ ethenyl, y ¹ 1, y ² 0, x ¹ 21, x ⁴ and x ² 1, and R¹ is 4-C₆H₄, together with 15 g of a commercially available anti-migration agent and 2 g of monosodium phosphate, are stirred into a padding liquor so that their final volume is 1 liter. A 65:35 polyester / cotton blend fabric is impregnated with this padding liquor at 25 ° C, squeezed off to approx. 65% liquid absorption, pre-dried in an infrared dryer for 30 seconds, dried for 60 seconds at 110 ° C and the disperse dye at 210 ° C fixed in the polyester fiber for 60 sec. The pre-dyed mixed fabric is then subjected to the dyeing conditions of a subsequent reactive dyeing, but without dye. For this purpose, the blended fabric is padded at 25 ° C with a chemical bath containing 240 g / liter table salt, 15 g / liter soda, 11.3 g / liter 50% sodium hydroxide solution and 4 g / liter an oxidizing agent based on benzenesulfonic acid derivative. Squeezed to 90-100% liquid absorption and steamed at 102-105 ° C for 45 seconds. Finally, the blended fabric is rinsed in hot water and dried.

A coloring that for comparison without adding a compound of the general formula I was carried out clearly cloudy. Then the percentage of cotton with a mixture of the commercial forms of C.I. Reactive Blue 19 and 220 dyed to the same shade, the entire coloring is also duller if not an aid the general formula I was used.

The effect can be illustrated by the fact that the Cotton content of the blended fabric after dyeing Dissolved sulfuric acid. The remaining polyester content is much more brilliant with the additive colored than without it.  

If pure cotton, e.g. B. Cotton poplin as above described impregnated with the padding liquor, fixed and aftertreated, is when the dye used Aid does not contain, the substrate stained gray, at Aid additive, however, almost white.

If the compound of the general formula I is replaced in Example 1 by the further compounds of the general formula I listed in Table 1, good results as in Example 1 are obtained in comparison to the dyeings without auxiliaries.

Example 30

Instead of 30 g of a liquid commercial form of C.I. Disperse Blue 165 30 g of a liquid, approx. 16% Commercial form of disperse red containing pure dye 184 colored as indicated in Example 1, so you get a clearer red polyester color after the cotton has been released or when trying to dye pure cotton, significantly less staining than without use of the aid.

Example 31

1 g of the above-mentioned liquid commercial form of C.I. Disperse Blue 165 and 0.2 g of the above liquid Commercial form of C.I. Disperse Red 184 are used together with 1 g of the compound of general used in Example 1 Formula I dispersed in 2000 g of water. The dispersion is with 4 g of ammonium sulfate, 2 g of a commercially available Dispersant based on a condensation product from naphthalenesulfonic acid sodium salt and Formaldehyde and 2 g of a condensation product m-cresol, formaldehyde and sodium sulfite added and with Acetic acid adjusted to pH 5.5. In that way dye liquor obtained is brought 100 g of a 65:35 Polyester / cotton blend and dyes for 45 min. at 130 ° C. After rinsing, soaping and rinsing again the cotton content of the blended fabric with the commercial form re-colored by C.I. Reactive Blue 19. The coloring is again much more brilliant than without using the Aid of the general formula I.  

Example 32

From 400 g of a 10% alginate thickener, 5 g of a water softener based on polyphosphate, 5 g one Oxidizing agent based on benzenesulfonic acid derivative, 200 g of urea, 20 g of a 10% solution of an emulsifier based on fatty acid glycol ester, 240 g water, 100 g of gasoline and 30 g of sodium bicarbonate becomes a thickened stock produced. In 700 g of this stock thickening 2.25 g of a 40% solution of the compound general formula I, 15 g of the above liquid Commercial form of C.I. Disperse Blue 165 and 50 g of Commercial form of C.I. Reactive Blue 53 and 235 g water introduced and this base color using a Rouleaux Printing machine patterned on a polyester / cotton Mixed fabric applied. The dyes are then at 175 ° C through superheated steam 5 min. fixed, with water hosed, soaped and rinsed.

The print is much more brilliant than without the use of the aid of the general formula I.

Example 33

0.8 g of a commercially available powder formulation from C.I. Disperse Red 358 together with 0.8 g of a 40% aqueous solution of the compound used in Example 1 of the general formula I dispersed in 2000 g of water. The dispersion is mixed with 2 g of ammonium sulfate and 4 g of one Carriers based on methylnaphthalene added and with Acetic acid adjusted to a pH of 5. In that way dye liquor obtained is brought 100 g of a 50:50 Polyester / wool blend and dyes for 1 hour at 106 ° C. After rinsing, soaping, rinsing and Drying gives a red color that is clear is clearer than the one without the addition of the aid is obtained.  

Example 34

According to Example 1, thermosol staining is shown Polyester / cotton blend, but without those there Compound of the general already present during the dyeing process Formula I, created. Rather, this connection becomes the chemical bath in a concentration of 4 g / l added and proceed as described in Example 1.

Here too you get a coloring that is much more brilliant occurs as the one without using the connection of the general formula I.

Claims (10)

1. A process for dyeing and printing mixed fabrics made of polyester and natural fiber materials, characterized in that one or more compounds of the general formula I in the dye baths, padding liquors or printing pastes are included in what
R and R ′ independently of one another are hydrogen, linear or branched alkyl having 1 to 18 carbon atoms, which is optionally substituted by chlorine, bromine or alkoxy having 1 to 4 carbon atoms; Cyclopentyl; Cyclohexyl; Allyl; Methallyl; Acrylic; Methacrylic; Crotyl; Phenyl which is mono- or disubstituted by chlorine, bromine, methyl, alkoxy having 1 to 4 carbon atoms, where x ⁵ is a number from 1 to 10, benzyl or COR ″, where R ″ can have one of the meanings of R, but is independent of it,
D¹ to D⁵ linear (C₂-C₁₀) - or cyclic (C₃-C₁₀) - alkylene units which are unsubstituted or by (C₁-C₄) alkyl, (C₁-C₄) alkoxy or wherein p stands for a number from 0-10, are substituted, or in which D⁶ has the same meanings as this independently of D¹ to D⁵ and x ⁶ is a number from 1 to 100, where all groups D¹ to D⁵ can be interchanged as desired within an idealized molecule of the general formula I and thus a static distribution subject to
x ¹ to x ⁵ independently of one another are a number from 1 to 100, means
R¹ 1.4-phenylene, 1.2-phenylene, 1.3-phenylene, 1.4-naphthylene, 1.8-naphthylene, 2.2'-, 2.4'-, or 4.4'-biphenylene, lienaric or branched alkylene with 2 to 18 carbon atoms or cyclic alkylene with 4 to 6 carbon atoms, where all R¹ may be optionally substituted by at least one group SO₃M or COOM, where M is hydrogen, a cation from the series of alkali metals or a cation from the series of ammonia, primary, secondary, tertiary or quaternary amine; or by where the last radical is substituted at the same time by two radicals R 1 and w is a number from 1 to 5, the radicals R 1 being subject to a static distribution and
y 1 and y 2, independently of one another, mean a number from 0 to 20, provided that the sum y 1 + y 2 is 0 to 20. 2. Procedure according to claim 1, characterized in that R, R 'and R ″ are hydrogen or methyl. 3. The method according to claim 1 and / or 2, characterized characterized in that D¹ to D⁶ ethylene, 1,2-propylene or 1,4-butylene. 4. The method according to one or more of claims 1 to 3, characterized in that x ¹ and x ³ to x ⁶ 1 to 80 and x ² represent 1 to 4. 5. The method according to one or more of claims 1 to 5, characterized in that R¹ is 1,4-phenylene, 1,3-phenylene or 1,2-phenylene means. 6. The method according to one or more of claims 1 to 6, characterized in that y ¹ and y ² represent 1 to 10. 7. The method according to one or more of claims 1 to 6, characterized in that blended fabrics made of polyester and cellulose dyed or printed. 8. The method according to claim 7, characterized in that that the cellulose portion is colored with reactive dye becomes. 9. The method according to claim 7, characterized in that the polyester content according to the so-called thermosol process is colored. 10. The method according to one or more of claims 7 to 9, characterized in that the polyester content is dyed before the cellulose content.