DE4445930A1 - Printing cellulose textile uses base-relating fixative for reactive dye - Google Patents

Abstract

In printing textiles consisting of cellulose fibres, opt. mixed with other fibres, with reactive dyes, the base-releasing cpd. used for fixing comprises salt(s) (I) of satd. and/or unsatd. beta -alkoxy-carboxylic acids of formulae (IA) and (IB), where R<1>, R<2> = 1-3C alkyl or R<1> + R<2> = -CH2CH2-; R<3> = H or 1-3C alkyl; R<4> = H, 1-3C alkyl, phenyl or benzyl; Me = 1 equiv. of an alkali(ne earth) metal or an ammonium gp. of the formula NHA<1>A<2>A<3> (A<1>,A<2>,A<3> = H, Me, Et or C2H4OH). Pref. (IA) is the Na or K salt of 3,3-di(m)ethoxybutanoic acid.

Description

The invention relates to a method for printing on textiles Materials made from cellulose fibers or cellulose fibers mixed with other fibers, with reactive dyes fabrics and fix the dyes with compounds that are under release a base under the fixing conditions.

When dyeing and printing textile materials that come from Cellulose fibers exist or cellulose fibers in a mixture with contain other fibers with reactive dyes Fixation of the reactive dyes on the cellulose fibers alkali conditions. For example, you add soda to a print paste containing a reactive dye with monochlorotriazine groups Contains anchor. Reactive dyes, the vinyl sulfone groups as In contrast, anchors are little against alkalis stable, so that printing pastes containing such a reactive dye and contain alkali, must be consumed as soon as possible. Printing pastes containing reactive dye with a vinyl sulfone group Anchors contain, but can then several at room temperature Can be stored for days when they are neutral at room temperature active agent included, but under the fixing conditions gen, d. H. for example when steaming, quickly disintegrates and an al forms calic medium. One such example is Sodium trichloroacetate. However, this product has the disadvantage that in addition to the formation of alkali, large amounts of chloroform are released the one that heavily pollutes the exhaust air of the print shop.

Sodium trichloroacetate is used for example in direct printing Dyes with vinyl sulfone group anchors or also with reactive Reserve printing process used. With the reactive reserve pressure ver the textile is pre-padded with a dye liquor that a reactive dye with vinyl sulfone group anchor and sodium contains trichloroacetate as an alkali donor, then dried and then overprinted with a printing paste that contains a dye with a monochlorotriazine group as an anchor and a reservation contains agents for the fund dyes.

In the simplest case, sodium bicarbonate is used as the compound used, which releases alkali under fixing conditions.

Sodium bicarbonate increases the alkali during the steaming process of the medium, but reacts alka at room temperature lish. The shelf life of being set with sodium bicarbonate  This limits printing pastes. Such pastes must be used with reactive dyes that are already on ge small amounts of alkali react sensitively, even on the day of Preparation to be processed. The reactive reserve pressure at which the textile material is first pre-treated with a reactive dye blocks that contains a vinyl sulfone group anchor is at for example with sodium bicarbonate not at all feasible because the dye is already fixed during drying and can therefore no longer be fully reserved.

DE-A 43 06 433 describes a method of printing flä contain cellulose fiber materials or cellulose fibers the materials with reactive dyes using one phase ink jet process or other non-contact Minimal application spray technique and subsequent fixation of the Reactive dyes known on the fiber, in which an aqueous Ink formulation that uses an alkali fluoride, an alkali formate, an alkali citrate, an alkali salt of a C₂ bis C₄-dicarboxylic acid or a mixture of the alkali salts mentioned ent holds. The disadvantage of these agents is that they are only at very high temperatures to decompose with the formation of alkali. Among the usual Fixing conditions for reactive dyes, e.g. B. 6-12 min at 102 ° C in saturated steam or 5 minutes at 150 ° C hot air, none is sufficient rapid alkali formation instead.

The invention has for its object for printing on textile materials consisting of cellulose fibers or Contain cellulose fibers mixed with other fibers with To provide reactive dyes such compounds those in aqueous medium at room temperature at a pH of 7 are stable and which under the conditions of the reactive dye Rapidly form an alkaline medium.

The object is achieved with a method for Printing on textile materials made from cellulose fibers stand or ent cellulose fibers in a mixture with other fibers hold with reactive dyes and fix the dyes with Compounds that release a base under the fixing conditions set when substances releasing bases as the formula

in the
R¹, R² = C₁- to C₃-alkyl or together form an ethylene group,
R³ = H or C₁ to C₃ alkyl,
R⁴ = H, C₁ to C₃ alkyl, phenyl or benzyl and
Me = alkali metal, alkaline earth metal or ammonium equivalent of the formula NHR¹R²R³ with R¹, R², R³ = H, CH₃, C₂H₅- or C₂H₄OH,
Substances of the formula

in the
R¹ = C₁ to C₃ alkyl,
R³ = H or C₁ to C₃ alkyl,
R⁴ = H, C₁ to C₃ alkyl, phenyl or benzyl and
Me = alkali metal or alkaline earth metal or ammonium equivalent of the formula NHR¹R²R³ with R¹, R², R³ = H, CH₃, C₂H₅- or C₂H₄OH mean, or mixtures of substances I and II.

The invention also relates to the use of Compounds of the formula

in the
R¹, R² = C₁- to C₃-alkyl or together form an ethylene group,
R³ = H or C₁ to C₃ alkyl,
R⁴ = H, C₁ to C₃ alkyl, phenyl or benzyl and
Me = alkali metal, alkaline earth metal or ammonium equivalent of the formula NHR¹R²R³ with R¹, R², R³ = H, CH₃₁ C₂H₅- or C₂H₄OH mean, and / or

in the
R¹ = C₁ to C₃ alkyl,
R³ = H or C₁ to C₃ alkyl,
R⁴ = H, C₁ to C₃ alkyl, phenyl or benzyl and
Me = alkali metal, alkaline earth metal or ammonium equivalent of
Formula NHR¹R²R³ with R¹, R², R³ = H, CH₃, C₂H₅- or C₂H₄OH be mean
as base releasing compounds when fixing reactive dyes on cellulose fibers.

The compounds of the formulas I and II are, for example, by Ketalization of the carbonyl group of β-ketocarboxylic acid esters and subsequent saponification of the esters in the alkaline pH range aqueous medium. The carbonyl group of the keto esters can be converted into ketal groups by all known methods be, e.g. B. by the action of monohydric C₁ to C₃ alcohols in the presence of acids or by reaction with orthoesters. Suitable ortho-esters are, for example, ortho-formic acid esters, ortho-acetic acid esters and ortho-propionic acid esters. Before added ketocarboxylic acid esters are methyl acetoacetate esters and ethyl acetoacetate.

In the above formulas I and II, Me means an alkali metal or alkaline earth metal equivalent. Suitable alkali metals are, for example, lithium, sodium and potassium. From the earth Alkali metals preferably contain magnesium and calcium ions Consideration. The ammonium salts are preferably ammonia, methyl amine, dimethylamine, trimethylamine, ethylamine, diethylamine, tri methylamine, ethanolamine, diethanolamine or triethanolamine as Bases. As base-releasing compounds of the formula I. the sodium or potassium salts are preferably used 3,3-dimethoxybutanoic acid or 3,3-diethoxybutanoic acid. In the Mixtures are often produced from ketals Compounds of formulas I and II. These mixtures can in  any ratio as base releasing compounds used to fix reactive dyes on cellulose fibers be set. In formula I, the substituents R¹ and R² together form an ethylene group. Such connections will be prepared, for example, by methyl acetoacetate ester with ethylene glycol in the presence of sulfuric acid ketali siert.

The compounds of the formulas I to be used according to the invention and II come as base releasing compounds for fixation reactive dyes on cellulose fibers. The Art the dyeing or printing process with which the reactive dyes are not applied to the textile material Role. One can use the base releasing compounds, for example wise in direct printing, in reserve printing with reactive dyes or use with ink jet single-phase reactive printing. By particular Rem is interested in the use of ver according to the invention turning compounds I and II at the reserve pressure with reactive dyes. With reactive reserve printing, this is what is to be printed Material first padded with a block fleet, one Reactive dye, e.g. B. one with a vinyl sulfone group anchor and at least one compound of the formula I and / or II in aqueous solution. The pH of this log float ten, which may also contain other substances, e.g. B. Defoamer, oxidizer and leveling agent is preferred wise in the neutral area. Such block fleets last for days durable.

The textile material padded with the fleet described above is then dried and then with a printing paste that a reactive dye with, for example, a monochlorotriazine group anchor as well as a reservation agent or just a re contains preservative, printed according to pattern, then dried and fixed and washed. Those to be used according to the invention Compounds I and II disintegrate under the fixing conditions, e.g. B. in saturated steam, d. H. at temperatures above 100 ° C quickly and produce brilliant and colorful textile prints. The connections of the formula I and II are, for example, in amounts of 10 to 150, preferably 20 to 80 g / l in the padding liquor or in the pressure paste included.

The textile materials consist of cellulose fibers or ent keep cellulose fibers mixed with other fibers. In the event of of fiber blends contain the textile materials alongside Cellulose fibers mainly polyamide fibers or polyester fibers. Mixed fabrics made of polyester and Cotton. The textile materials can, for example, as Ge  knit, woven or as nonwovens. Reactive dyes that used for dyeing cellulose fibers are known and commercially available. They are detailed in the Color Index, 1982, 3rd Edition, Vol 5, published by the Society of Dyers and Colourists, H. Charlesworth & Co. Ltd., Huddersfield. For printing and dyeing cellu textile materials the quantities normally considered are loosened Dyes and any auxiliaries to be used medium used in the usual amounts. The reactive dyes can different reactive groups, referred to above as anchors be net, have z. B. vinyl sulfone, monochlorotriazine or β-sulfatoethylsulfonyl groups. The dyes can be different belong to dye classes, e.g. B. azo dyes, Metallkom plex azo dyes, anthraquinone dyes, phthalocyanine dyes substances, phenacen and azomethine dyes.

If printing with a printing paste or ink form lation is carried out, they contain an aqueous solution a reactive dye and at least one compound of Formula I and / or formula II in an amount of, for example 10 to 150 g / l. The printing pastes or inks can optionally contain other common additives, e.g. B. at least one Disper sion dye to blend fabrics made of cellulose fibers and polyester to dye fibers or other common additives such as emulsifiers, Defoamers or polar organic solvents such as B. Ethylene glycol, to improve running properties.

Since the compounds of the formulas I and II a non-alkali in aqueous solution at room temperature have pH and since they are under the conditions of Fix the reactive dyes quickly an alkaline medium form, the printing pastes are stable and at room temperature deliver brilliant and colorful textile prints.

The percentages in the examples mean percent by weight.

Examples

Preparation of the base releasing compounds, hereinafter Called alkaline dispenser.

Alkaline dispenser 1

In a flask with a stirrer and a distillation bridge is provided, 169.2 g (1.30 mol) of ethyl acetoacetate, 400 ml of ethanol and 0.5 ml of boron trifluoride in methanol. At room temperature, add with stirring within 90 minutes 192.7 g (1.3 mol) triethyl orthoformate. The reaction  mixture is heated to 40 ° C and at this temperature for as long stirred until the ethyl acetoacetate has reacted completely Has. Then 2 ml of 50% aqueous sodium hydroxide solution are added and distilled off the ethyl formate and ethanol in vacuo. The remaining sump consists of 3,3-diethoxybutanoic acid ethyl ester and 3-ethoxy-but-2-enoic acid ethyl ester in a molar ratio of 2: 1.

The sump is washed with 200 ml of distilled water and 104.0 g (1.30 mol) 50% aqueous sodium hydroxide solution added, and at 70 ° C. stirred until the esters are completely saponified. Now is adjusted to pH = 7 with a little 1N hydrochloric acid. The Reacti mixture is then on the rotary evaporator at an In temperature of 50 ° C and a pressure of 1 mbar then 12 hours at a bath temperature of 50 ° C under one Pressure of 50 mbar dried. 225 g of a white pulp are obtained vers from a mixture of 3-ethoxy-but-2-ene acid sodium salt and 3,3-diethoxybutanoic acid sodium salt in a molar ratio of 2: 1 Yield is 95% of theory.

Alkaline dispenser 2

In a flask equipped with a stirrer and distillation attachment is, 522.5 g (4.5 mol) of methyl acetoacetate and Submitted 1.0 ml of concentrated sulfuric acid and on a Temperature of 70 ° C heated. Once that temperature is reached 477.5 g (4.5 mol) of trimethyl are added within 150 minutes orthoformate and distilled the resulting by-products methanol and methyl formate from the reaction mixture. After the addition of the Tri methyl orthoformate, the reaction mixture at 180 minutes stirred at a temperature of 80 ° C and then at room temperature cooled down. The remaining methanol and Formic acid methyl esters are at room temperature under one Distilled off pressure of 1 mbar.

To saponify the esters, 460.0 g are added to the reaction mixture (4.5 mol) 50% aqueous sodium hydroxide solution, the mixture is heated to 50 ° C and stir at this temperature until the Esters are saponified. Now with a little 1N hydrochloric acid to pH = 7 set. Then the resulting from the saponification Methanol and the water introduced with the sodium hydroxide solution largest parts under a pressure of 50 mbar from the reaction mixed distilled off. The distillation will stop as soon as that Product starts to crystallize. After cooling the reak tion mixture to room temperature, 2.5 l of acetone are added, where A voluminous precipitate is formed, which is suctioned off and mixed with 2 l Washed acetone. After the precipitation has dried in  Vacuum drying oven at 50 mbar and 75 ° C gives approx. 500 g a white powder made from a mixture of 3-methoxy but-2-ene acid sodium salt and 3,3-dimethoxybutanoic acid sodium salt in a molar ratio of 1: 1. The yield is 75% of the Theory.

Alkaline dispenser 3

In a flask with a stirrer, distillation attachment and a dropping funnel, 522.5 g (4.5 mol) of acet ethyl acetate and 0.5 ml of boron trifluoride in methanol sets and with stirring at room temperature within 2 hours treated with 477.5 g (4.5 mol) of triethyl orthoformate. The Reacti on mixture is then heated to a temperature of 50 ° C and so long at this temperature until the acetoacetic acid ethyl ester has completely reacted. The reaction mixture turns on then heated to a temperature up to 90 ° C to ants acid ethyl ester and ethanol to be distilled off from the reaction mixture lieren. The residue is then distilled in vacuo. Of the Ester boils under a pressure of 3.0 mbar and a temperature of 41 ° C. 191.8 g are obtained, corresponding to a yield of 95%. of theory, on colorless crystals with an anise-like odor.

150 g of the ester described above are in a flask Submitted 200 ml of distilled water and then with 75.4 g (0.94 mol) 50% aqueous sodium hydroxide solution was added dropwise. The reaction mixture is heated to a temperature of 70 ° C. and stir at this temperature until the ester is complete is saponified. Now the pH is adjusted to 7 with a little 1N hydrochloric acid poses. The mixture is then on a rotary evaporator under a pressure of 1 mbar and a temperature of 50 ° C. constricted and dried for 12 hours at 50 ° C and a pressure of 50 mbar net. 136 g of the sodium salt of 3-ethoxy-but-2-ene are obtained acid in the form of a yellowish powder in a yield of 94% of theory.

Alkaline dispenser 4

In a flask with a water separator and a back flow cooler is provided, 174.2 g (1.5 mol) of acetoacetic acid methyl ester, 111.7 g (1.8 mol) ethylene glycol, 0.15 g p-toluenesul fonic acid and 225 ml of toluene and while boiling on Keep reflux until no more water of reaction separates. The reaction mixture is then - after distilling off Toluene - distilled in vacuo. It boils under pressure from 10 mbar at a temperature of approx. 80 ° C.  

200 ml of water and 0.82 mol of the butanoic acid methyl ester-2-ethylene ketals are in a flask equipped with a stirrer submitted. 65.9 g (0.82 mol) of 50% strength aqueous sodium hydroxide are added dropwise lye, the reaction mixture is heated to 50 ° C. and stirred long at this temperature until the ester is completely saponified is. Now adjust to pH = 7 with a little 1N hydrochloric acid. The The reaction mixture is then on a rotary evaporator at one pressure of 1 mbar and a temperature of 50 ° C and then 12 hours in a vacuum drying cabinet at a pressure of 50 mbar and a temperature of 50 ° C dried. 153.1 g of Bu are obtained tanoic acid-2-ethylene ketal sodium salt in the form of a yellowish pul verse.

example 1

To perform a reserve print with reactive dyes, you first put a padding fleet of the following composition forth:

40 g of the black reactive dye of the CI Reactive Black 5
30 g of the brown reactive dye of the CI Reactive Brown 21
850 g water
10 g of 3-nitrobenzenesulfonic acid, sodium salt
10 g of a copolymer of acrylic acid and acrylamide and
60 g alkaline dispenser 1
1000 g

After padding with the padding fleet specified above, this will be Cotton fabric dried for 2 minutes at a temperature of 100 ° C and then according to the pattern with a colored reserve and then with printed with a white reserve. The Buntreserve has the following together composition:

700 g of an alginate thickener (5% in water)
5 g sodium hexametaphosphate
10 g of 3-nitrobenzenesulfonic acid sodium salt
100 g urea
30 g soda
30 g of the yellow reactive dye CI Reactive Yellow 151
60 g 1.1 ′, 1 ′ ′ - NITRILOTRIETHANSULFONSAURES KALIUM and
65 g water
1000 g

The white reserve has the following composition:

700 g of an alginate thickener (5% in water)
5 g sodium hexametaphosphate
10 g sodium 3-nitrobenzenesulfonic acid
100 g urea
30 g soda
60 g 1.1 ′, 1 ′ ′ - NITRILOTRIETHANSULFONSAURES KALIUM and
95 g water
1000 g

After the overprint with the color reserve and the white reserve the printed textile material for 2 minutes at a temperature of 100 ° C dried and then in saturated steam at 10 minutes Fixed at 102 ° C, then cold, then boil with rinsed in the water, then boiling with a neutral detergent soaped and then rinsed cold. You get one out spoken brilliant and contour-sharp reactive reserve pressure. The fund appears uniformly deep black. The pattern of the over prints are clear in color. The white reserve is pure white without every gray veil.

Example 2

Example 1 is repeated with the only exception that the Block liquor instead of the alkali dispenser 1 now the alkali contains donor 2. A perfect pressure drop results.

Example 3

Example 1 is repeated with the exception that instead of Alkali dispenser 1 now uses the alkali dispenser 3. The pressure result corresponds approximately to that of example 1.

Example 4

Example 1 is repeated with the exception that instead of Alkali dispenser 1 now uses the alkali dispenser 4. The pressure paste was stable for several days and gave a satisfactory result printing result.

Comparative Example 1

The reserve print with reactive ink described in Example 1 was repeated with the only exception that one was place the same amount of the alkaline dispenser 1 in the block liquor  of sodium trichloroacetate. One also received a brilliant reactive reserve pressure, but achieves that black fund not the color depth of the fund as in example 1. He is also somewhat bluish. The white reserve is pure white, the Color reserves are pure in color. The steaming process occurs clear smell of chloroform, so this way of working can only be carried out with good ventilation.

Comparative Example 2

The reserve pressure described in Example 1 was the only one repeated the exception that instead of the alkali donor 1 in the Padding liquor was now used 30 g of sodium hydrogen carbonate. A deep black fund was obtained. The white reserve reached however only a gray-blue hue. The colored reserves appeared bluish and cloudy.

Example 5

Determination of the durability of printing pastes, the reactive dyes with vinyl sulfone groups as anchors. First, the Master batches A and B from those given in the following overview components:

Each of 960 g of stock batch was combined with 40 g of the one below mentioned dyes printing pastes. The printing pastes were immediately, after 3, 6, 9, 13 and 16 days on cotton prints, dried for 1 min at 100 ° C and then 10 min at 102 ° C in Saturated steam fixed.

The color strengths determined with the individual dyes are in given in Table 1.  

table

Color strengths with

As can be seen from the table above, the di right after starting with the different master batches A and B printing pastes obtained for the three dyes used each because of a comparable depth of color and brilliance. The blue color However, substance falls into the formulation with the parent batch A. the color strength slightly.

After 3, 6, 9, 13 and 16 days, those printing pastes drop Contain sodium bicarbonate as an alkali dispenser (manufactured increasingly from the master batches A) in the color strength. The Printing paste from the yellow reactive dye in master batch A er seems uneven and spotty and results in a color weak print. The printing pastes used with master batch B change practically not in the period examined.

Claims (3)

1. Process for printing on textile materials which consist of cellulose fibers or contain cellulose fibers in a mixture with other fibers, with reactive dyes and fixing the dyes with compounds which release a base under the conditions of fixation, characterized in that substances which release bases are used as bases of the formula in the
R¹, R² = C₁- to C₃-alkyl or together form an ethylene group,
R³ = H or C₁ to C₃ alkyl,
R⁴ = H, C₁ to C₃ alkyl, phenyl or benzyl and
Me = alkali metal, alkaline earth metal or ammonium equivalent of the formula
NHR¹R²R³ with R¹, R², R³ = H, CH₃, C₂H₅ or C₂H₄OH,
Substances of the formula in the
R¹ = C₁ to C₃ alkyl,
R³ = H or C₁ to C₃ alkyl,
R⁴ = H, C₁ to C₃ alkyl, phenyl or benzyl and
Me = alkali metal, alkaline earth metal or ammonium equivalent of the formula NHR¹R²R³ with R¹, R², R³ = H, CH₃, C₂H₅ or C₂H₄OH or mixtures of substances I and II. 2. The method according to claim 1, characterized in that one as substances of formula I the sodium or potassium salts 3, 3-dimethoxybutanoic acid or 3,3-diethoxybutanoic acid puts. 3. Use of compounds of the formula in the
R¹, R² = C₁- to C₃-alkyl or together form an ethylene group,
R³ = H or C₁ to C₃ alkyl,
R⁴ = H, C₁ to C₃ alkyl, phenyl or benzyl and
Me = alkali metal, alkaline earth metal or ammonium equivalent of the formula NHR¹R²R³ with R¹, R², R³ = H, CH₃, C₂H₅ or C₂H₄OH, and / or in the
R¹ = C₁ to C₃ alkyl,
R³ = H or C₁ to C₃ alkyl,
R⁴ = H, C₁ to C₃ alkyl, phenyl or benzyl and
Me = alkali metal, alkaline earth metal or ammonium equivalent of the formula NHR¹R²R³ with R¹, R², R³ = H, CH₃, C₂H₅ or C₂H₄OH mean, as base-releasing compounds when fixing reactive dyes on cellulose fibers.