EP1713866A1

EP1713866A1 - Aqueous liquid composition comprising dyes

Info

Publication number: EP1713866A1
Application number: EP05702199A
Authority: EP
Inventors: Ludwig Hasemann
Original assignee: Clariant International Ltd
Current assignee: Clariant Finance BVI Ltd
Priority date: 2004-01-23
Filing date: 2005-01-06
Publication date: 2006-10-25
Also published as: BRPI0507084A; WO2005080509A1; CN1910242A

Abstract

An aqueous liquid composition comprising a reactive dye and alkali metal polyacrylates or methacrylates with number average degree of polymerization not exceeding 1000 and 2-(2-Diethylaminoethoxy)ethanol having high storage stability.

Description

Aqueous Liquid Composition Comprising Reactive Dyes

The present invention relates to an aqueous liquid composition comprising a reactive dye having high storage stability.

Industrial dyeing and printing with a reactive dye have been carried out usually in an aqueous medium, and therefore dyes commercially available in the form of powder or granule must be dissolved in hot water to be subjected to the aqueous medium dyeing and printing.

Recently, development of dyes in a form suitable for an automatic weighing system has been required increasingly, because a dye house has been actively automated in many aspects.

An aqueous liquid dye composition is now noticeable, because it makes no dust when handled and has no pollution problem on an operation environment, it requires no dissolving process to contribute to a labour- and energy-saving, and moreover it is suitable for the automatic weighing system. Thus, an aqueous liquid dye composition with no problem from industrial point of view has been required eagerly to be developed.

A reactive dye-containing aqueous liquid composition can be prepared relatively easily, when the reactive dye has a high water solubility. However, there are many reactive dyes having a water solubility which is not high enough to form the aqueous liquid composition easily. Therefore, in order to improve the water solubility of reactive dyes, there have heretofore been proposed many attempts including addition of various kinds of hydrotropic agents, removal of inorganic salts contained in the dyes or the like. The reactive dye-containing aqueous liquid composition prepared in such a manner is rather stable at ambient temperature. From industrial of view, however, it is usually left at a relatively low temperature such as 0 °C or lower, or a relatively high temperature such as 40 °C or higher through manufacture, custody, transportation including shipping, storage and the like. For this reason, a storage stability at a relatively low or high temperature is a serious problem from industrial point of view. Particularly, at a relatively high temperature, the reactive dye is, as known, subject to chemical change, i.e. hydrolysis. Therefore, storage for a long period of time at a relatively high temperature causes troubles such that dyeing or printing in any known manner only gives dyed or printed products of a color different from that expected.

On the other hand, storage of the reactive dye-containing aqueous liquid composition at a relatively low temperature causes troubles such that the reactive dyes precipitate or the aqueous liquid composition turns to a paste-like composition due to the lowering of water solubility of the reactive dyes or the salting-out effect of the inorganic salts contained therein, and moreover the precipitate-containing or paste-like composition once formed hardly turns to the original clarified liquid composition, so that an extraordinary time should be required for the preparation of dye bath, and the reproductivity of dyeing can hardly be obtained.

In order to provide a reactive dye-containing aqueous liquid composition having high storage stability, there have heretofore been made many attempts, which are still not satisfactory from industrial point of view.

Liquid compositions of reactive dyestuffs, in particular, lose their reactivity to cellulose fibre by a hydrolysis of their reactive groups (spontaneous decomposition), so that troubles derived from reduction of the dye exaustion by fibre are frequently experienced. Consequently, on preparing liquid compositions of reactive dyestuffs, buffers to maintain a certain pH value and/or chelating agents to prevent influences of alkaline earth metal ions such as calcium ion and magnesium ion, may be added.

As those buffers and chelating agents, phosphates such as sodium phosphate, potassium phosphate are often used.

When phosphates are used for preparation of liquid compositions of reactive dyestuffs, they are not so much able to inhibit the decomposition of reactive groups of reactive dyestuffs, and after the liquid compositions thus obtained are stored for a long term, the phosphates tend to crystalize out. Moreover, use of phosphates is, in itself, unfavorable from point of view of environment pollution.

Usual additives to improve the solubility such as N-methyl pyrrolidone, ε-caprolactam may promote the decomposition of the reactive group.

It is an object of the present application to provide liquid formulations of reactive dyestuffs having a prolongated physical stability and a prolongated chemical stability.

It has been surprisingly found that liquid formulations comprising reactive dyestuffs and an alkali metal polyacrylates or methacrylates with number average degree of polymerization not exceeding 1000 and 2-(2-Diethylaminoethoxy) ethanol do not cause to decompose the reactive groups of the reactive dyestuffs, and exhibit extremely high storage-stability to aging.

As a reactive dyestuff which is used in the present invention, there may be mentioned a water-soluble reactive dyestuff containing one to four reactive halogen atoms capable of reacting with a textile fibre which is mentioned in the Colour Index. Desirable reactive dyestuffs to obtain the liquid compositions of the present invention are reactive dyestuffs having one or two triazinyl group(s) which carry one or two chlorine atom(s) or which carry one or two chlorine atom(s) respectively as a reactive group(s). However, the present invention is not limited thereby and may be applied to any reactive-dyestuffs provided for the above-mentioned conditions.

Preferred dyestuffs according to the according to the invention bear at least one reactive group and are compounds of the formula formula (I)

Chromophor

wherein the Chromophore is the radical of a monoazo dye of the formula

in which K is a radical of the benzene or naphthalene or benzochinone series or a heterocyclic radical and (R₃)_n and (P are n = 0 to 3 and m = 0 to 6 identical or different substituents chosen from the group consisting of Ci -C₄ alkyl, Ci -C₄ alkoxy,

C₂ -C₄ alkanoylamino, ureido, halogen, carboxyl and sulfo, or the Chromophore is the radical of a polyazo, metal complex azo, anthraquinone, formazan, phthalocyanine or dioxazine dye;

Y is chlorine or fluorine;

X is -NR₁R₂ wherein, Ri is H; C_1-6alkyl; substituted C_1-6alkyl or Cι_₆alkyl, which is interrupted by one or more atoms from the group consisting of O, N and S; R₂ is H; C_1-6alkyl; substituted C_1-6alkyl; C_1-6alkyl, which is interrupted by one or more atoms from the group consisting of O, N and S or phenyl which is substituted by one or more carboxy, sulfo, C_Malkyl and/or Ci^alkoxy; or Ri and R₂ together with the nitrogen atom form a 5, 6 or 7 membered heterocyclic ring which optionally can contain more than one heteroatom from the group consisting of N, O and S and which may be additionally substituted by a C_1-2alkyl-OH group;

salts thereof and mixtures of these compounds.

The alkyl groups may be linear or branched. Preferred substituents for the alkyl groups are -OH, -COOH, -CN, halogen, -COOC_1-2alkyl, -SO₃H, -CONH₂, -NH₂, C_1-2alkoxy and/or NO₂.

Preferably compounds according to formula (I) wherein

Y is Chlorine; X is -NRiR₂ wherein, Ri is H; unsubstituted Cι- alkyl; C_1-4-alkyl which is monosubstituted or disubstituted by -COOH, -CONH₂, -SO₃H or -OH; R₂ is H; unsubstituted C_1-2alkyl; C_1-4-alkyl which is monosubstituted or disubstituted by -COOH, -CONH₂, -SO₃H or -OH or phenyl which is substituted by one or more carboxy, sulfo, and/or C_1-4alkoxy; or Ri and R₂ together with the nitrogen atom form a 6 membered hetero-cyclic ring which optionally can contain more than one hetero-atom from the group consisting of N, O and S and which may be additionally substituted by a C_1-2alkyl-OH group;

A ring wherein Ri and R₂ together with the nitrogen atom form a 6 membered hetero-cyclic ring in the substiuent of the formula -NRiR₂ which optionally can contain more than one hetero-atom is for example morpholino.

Preferred dyestuffs have one triazinyl group which carries one chlorine atom as a reactive group. More preferred dyestuffs are dystuffs according to the formula (I) or (II) or (III) or

(IV):

Moreover, the number average degree of polymerization of alkali metal polyacrylates or polymethacrylates used according to the present invention does not exceed 1000, preferably 100, and more preferably, is from 15 to 50. The acrylic acid and/or methacrylic acid may be copolymerized with copolymerizable monomer such as maleic acid and succinic acid in such small quantities as not cancel the effect according to this invention. By preference the percentage of copolymerizable monomer other than acrylic acid and/or methacrylic acid is less than 50%, more preferred less than 20%, and most preferred less than 5% of the total amount of monomers. As alkali metal in alkali metal polyacrylates or polymethacrylates, sodium, potassium or lithium is mentioned and sodium salts thereof are usually employed. The preferred polyacrylate and/or polymetacrylate are those which are completely neutralized by prefference with alkali hydroxide, more preferred with sodium hydroxide.

A mixture of the alkali metal polyacrylates and the alkali metal polymethacrylates may be also used and a mixture of two or more of reactive dyestuffs may be also used.

According to the invention 2-(2-Diethylaminoethoxy)ethanol is added to the dyestuff solution in order to improve the solubility. The combination of the polyacrylate as mentioned above and the 2-(2-Diethylaminoethoxy)ethanol gives improved chemical and physical stability to the dyestuff composition.

It is favorably prepared for the liquid compositions to comprise 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight of the alkali metal polyacrylates and/or polymethacrylates, 5 to 60% by weight, preferably 10 to 40% by weight of a reactive dyestuff and 35 to 90% by weight of water.

It is further favorable that the composition comprises 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight of the 2-(2-Diethylaminoethoxy)ethanol.

The liquid compositions of this invention maybe prepared by adding the alkali polyacrylates or polymethacrylates and the 2-(2-Diethylaminoethoxy)ethanol and water, and, if necessarily, also other additives to a reaction mixture containing reactive dyestuffs, or filter-cake obtained by filtration continued on salting-out.

To improve stability of the liquid compositions to aging, reaction solutions containing reactive dyestuffs or reactive dyestuff filter-cakes obtained by salting-out may be used after desalting and concentrating reaction solutions by passing them through separation membranes such as cellulose acetate membrane or polybenzimidazolone membrane (PBIL). The fiber-reactive dyestuff formulation according to the invention is useful for dyeing or printing or Inkjet printing hydroxy-group-containing or nitrogen-containing organic substrates. Preferred substrates are leather and fibrous materials which comprise natural or synthetic polyamides and, particularly, natural or regenerated cellulose such as cotton, viscose and spun rayon or papery products. The preferred substrates are textile materials comprising cotton. Further preferred substrates are paper or papery products or card-board.

Dyeing or printing may be carried out in accordance with known methods conventional in the fiber-reactive dyestuff field.

In a preferred dyeing process the exhaust-dyeing method is used at temperatures within the range of from 40 to 100°C, more preferably 50 to 80°C. In a preferred printing process, the padding method is used, for example pad-steam, pad-thermofix, pad-dry, pad-batch, pad-jig and pad-roll. Alternatively, printing may be carried out using ink-jet printing methods.

Moreover the fiber-reactive dyestuff formulation according to the invention may be used as or converted into a ink-jet printing ink.

Depending on the requirements the fiber-reactive dyestuff formulation according to the invention may be brought to the desired strength for example by dilution.

The ink composition and the printing pastes of the invention may further include as auxiliaries additional components which are normally used in inkjet inks or printing pastes, for example buffers, viscosity improvers, surface tension improvers, fixation accelerants, biozides, corrosion inhibitors, levelling agents, drying agents, humefactants, ink penetration additives, light stabilisers, UN absorbers, optical brighteners, coagulation reducers, ionic or nonionic surfactants and conducting salts. Examples

Example 1: 930 g press cake consisting essentially of the rective dye of the formula (I)

were dissolved in 4800 ml demineralized water and this solution was subjected to diafiltration at 25-50°C and applying pressure of 10-35 bar. After adding polyethoxylated triethanolamine hydrochloride the solution was subjected to a second diafiltration under the above mentioned conditions and concentrated. 2100ml of the concentrated solution was obtained. This solution is solution A which may be diluted with auxiliaries and water in order to obtain the desired strength.

To 350 ml of the above obtained dyestuff solution (solution A) were added 2,29 g SOKOLAN 20 (Trademark of BASF, SOKOLAN 20 is a polyacrylate which is completely neutralized with sodium hydroxide and which has an average mol weight of 2500) (which is equal to 5,1 g solution of SOKOLAN 20; 0,5 weight-%), 2,29 g 2-(2- diethylaminoethoxy)-ethanol (0,5 weight-%) and 0,69 g PROXEL GXL (0,15 weight-% ; Proxel GXL™; Proxel is a registered trademark of Zeneca AG Products, Inc. comprises l,2-benzisothiazoline-3-one (CAS-Number.: 2634-33-5). The solution is stirred. The pH-value was adjusted by adding 4,5 g of 10% HCl-solution to 7,5-7,7. This solution may be brought to the desired strengh by adding water.

This solution of example 1 (417 ml (458 g); comprising 17% dyestuff) does not show any precipitations after 12 weeks of storage at 0-5°C and 50°C (about 200ml of the solution were stored at 0-5°C and the other 200ml were stored at 50°C) and have still the same printing properties (printing loss: less then 10%) .

comparative example 1:

To 350 ml of the above mentioned solution A 2,29 g SOKOLAN 20 (trademark of BASF) (which is equivalent to 5,1 g solution of SOKOLAN 20; 0,5 weight-%) and 0.69 g PROXEL GXL (0,15 weight-%) were added and demineralized water is added in order to obtain the desired strengh.

The sample showed precipitations after one week at 0-5°C.

comparative example 2: To 350 ml of the above mentioned solution (solution A) 2,29 g SOKOLAN 20 (trademark of BASF) (which is equivalent to 5,1 g solution of SOKOLAN 20; 0,5 weight-%), 2,29 g N-Methylpyrrolidone (0,5 weight-%) and 0.69 g PROXEL GXL (0,15 weight-%) were added. The adjustment of the pH value was not necessary. The obtained solution was set to the standard by adding demineralized water. The sample clearly showed precipitations after three weeks at 0-5°C.

comparative example 3:

To 350 ml of the above mentioned solution (solution A) 2,29 g SOKOLAN 20 (trademark of BASF) (which is equivalent to 5,1 g solution of SOKOLAN 20; 0,5 weight-%), 4,58 g N-Methylpyrrolidone (1,0 weight-%) and 0.69 g PROXEL GXL (0,15 weight-%) were added. The adjustment of the pH value was not necessary. The obtained solution was set to the standard by adding demineralized water. The sample clearly showed precipitations after three weeks at 0-5°C.

comparative example 4:

To 350 ml of the above mentioned solution (solution A) 2,29 g SOKOLAN 20 (Trademark of BASF) (which is equivalent to 5,1 g solution of SOKOLAN 20 ; 0,5 weight-%), 2,29 g Caprolactame (0,5 weight-%) and 0.69 g PROXEL GXL (0,15 weight-%) were added. The adjustment of the pH value was not necessary. The obtained solution was set to the standard by adding demineralized water. The sample clearly showed precipitations after three weeks at 0-5°C.

comparative example 5:

To 350 ml of the above mentioned solution (solution A) 2,29 g SOKOLAN 20 (Trademark of BASF) (which is equivalent to 5,1 g solution of SOKOLAN 20; 0,5 weight-%), 4,58 g Caprolactame (1,0 weight-%) and 0.69 g PROXEL GXL (0,15 weight-%) were added. The adjustment of the pH value was not necessary. The obtained solution was set to the standard by adding demineralized water. The sample clearly showed precipitations after three weeks at 0-5°C.

Example 2:

520 g press cake consisting essentially of the rective dye of the formula (II)

were dissolved in 4000 ml demineralized water and this solution was subjected to diafiltration at 25-50°C and applying pressure of 10-35 bar and were concentrated after the diafiltration. 1060 ml of the concentrated solution was obtained. This solution is solution B which may be diluted with auxiliaries and water in order to obtain the desired strength.

To 265 ml of the above obtained dyestuff solution (solution B) were added 11,46 g SOKOLAN 25 CL GR (Trademark of BASF, SOKOLAN 25 CL GR is a polyacrylate which is completely neutralized with sodium hydroxide and which has an average mol weight of 4000) ( 3,0 weight-%) and 11,46 g 2-(2-diethylaminoethoxy)-ethanol (3,0 weight-%) and 0,69 g PROXEL GXL (0,15 weight-%; Proxel GXL™; Proxel is a registered trademark of Zeneca AG Products, Inc. comprises l,2-benzisothiazoline-3- one (CAS-Number.: 2634-33-5). The solution is stirred. The pH-value was adjusted by adding 2,25 g of 10% HCl-solution to 7,4-7,6. This solution may be brought to the desired strengh by adding water.

This solution of example 2 (345 ml (382 g); comprising 15% dyestuff) does not show any precipitations after 12 weeks of storage at 0-5°C and 50°C (about 170ml of the solution were stored at 0-5°C and the other 170ml were stored at 50°C) and have still the same printing properties (printing loss: less then 10%) .

comparative example 6: To 265 ml of the above obtained dyestuff solution (solution B) were added 11,46 g SOKOLAN 25 CL GR (Trademark of BASF) ( 3,0 weight-%) and 0,57 g PROXEL GXL (0,15 weight-%). The solution is stirred. The adjustment of the pH value was not necessary. This solution may be brought to the desired strengh by adding water. The sample clearly showed precipitations after two weeks at 0-5°C.

comparative example 7:

To 265 ml of the above obtained dyestuff solution (solution B) were added 11,46 g SOKOLAN 25 CL GR (Trademark of BASF) ( 3,0 weight-%) and 11,46 g N- Methylpyrrolidone (3% weight-%) and 0,57 g PROXEL GXL (0,15 weight-%). The solution is stirred. The adjustment of the pH value was not necessary. This solution may be brought to the desired strengh by adding water. The sample clearly showed precipitations after two weeks at 0-5°C.

comparative example 8: To 265 ml of the above obtained dyestuff solution (solution B) were added 11,46 g SOKOLAN 25 CL GR (Trademark of BASF) ( 3,0 weight-%) and 11,46 g Caprolactame (3% weight-%) and 0,57 g PROXEL GXL (0,15 weight-%). The solution is stirred. The adjustment of the pH value was not necessary. This solution maybe brought to the desired strengh by adding water.

The sample clearly showed precipitations after two weeks at 0-5°C.

Example 3:

860 g press cake consisting essentially of the rective dye of the formula (III)

were dissolved in 3200 ml demineralized water and this solution was subjected to diafiltration at 25-50°C and applying pressure of 10-35 bar and were concentrated after the diafiltration. 1560 ml of the concentrated solution was obtained. This solution is solution C which may be diluted with auxiliaries and water in order to obtain the desired strength.

To 390 ml of the above obtained dyestuff solution (solution C) were added 5,21 g SOKOLAN 20 (Trademark of BASF, SOKOLAN 20 is a polyacrylate which is completely neutralized with sodium hydroxide and which has an average mol weight of 2500) (which is equal to 11,58 g solution of SOKOLAN 20; 1,0 weight-%) and 5,21 g 2-(2-diethylaminoethoxy)-ethanol (1,0 weight-%) and 0,78 g PROXEL GXL (0,15 weight-%; Proxel GXL™; Proxel is a registered trademark of Zeneca AG Products, Inc. comprises l,2-benzisothiazoline-3-one (CAS-Number.: 2634-33-5). The solution is stirred. The pH- value was adjusted by adding 1,0 g of 10% HCl-solution to 7,4-7,6. This solution may be brought to the desired strengh by adding water.

This solution of example 3 (480 ml (521 g); comprising 15,6% dyestuff) does not show any precipitations after 12 weeks of storage at 0-5°C and 50°C (about 230ml of the solution were stored at 0-5°C and the other 230ml were stored at 50°C) and have still the same printing properties (printing loss: less then 10%) .

comparative example 9: To 390 ml of the above obtained dyestuff solution (solution C) were added 5,21 g

SOKOLAN 20 (Trademark of BASF) (which is equal to 11,58 g solution of SOKOLAN 20; 1,0 weight-%) and 0,78 g PROXEL GXL (0,15 weight-%). The solution is stirred. The adjustment of the pH value was not necessary. This solution may be brought to the desired strengh by adding water. The sample clearly showed precipitations after two weeks at 0-5°C.

comparative example 10:

To 390 ml of the above obtained dyestuff solution (solution C) were added 5,21 g SOKOLAN 20 (Trademark of BASF) (which is equal to 11,58 g solution of SOKOLAN 20; 1 ,0 weight-%) and 5,21 g N-Methylpyrrolidone (1 ,0 weigt-%) and 0,78 g PROXEL GXL (0,15 weight-%). The solution is stirred. The adjustment of the pH value was not necessary. This solution may be brought to the desired strengh by adding water. The sample clearly showed precipitations after four weeks at 0-5°C.

comparative example 11:

To 390 ml of the above obtained dyestuff solution (solution C) were added 5,21 g SOKOLAN 20 (Trademark of BASF) (which is equal to 11,58 g solution of SOKOLAN 20; 1,0 weight-%) and 5,21 g Caprolactame (1,0 weigt-%) and 0,78 g PROXEL GXL (0,15 weight-%). The solution is stirred. The adjustment of the pH value was not necessary. This solution may be brought to the desired strengh by adding water. The sample clearly showed precipitations after four weeks at 0-5°C.

Claims

1. Liquid formulations comprising at least one reactive dyestuff and an alkali metal polyacrylates or methacrylates with number average degree of polymerization not exceeding 1000 and 2-(2-Diethylaminoethoxy) ethanol.

2. Liquid formulations according to claim 1 characterized in that the composition comprises 5 to 60% by weight of at least one reactive dyestuff and 0.1 to 5.0% by weight alkali metal polyacrylates and/or polymethacrylates and 0.1 to 5.0% by weight 2-(2-Diethylaminoethoxy)ethanol.

3. Liquid formulations according to claim 1 characterized in that the at least one reactive dystuff is a reactive dyestuff having one or two triazinyl group(s) which carry one or two chlorine atom(s) or which carry one or two fluorine atom(s) respectively as a reactive group(s) .

4. Liquid formulations according to claim 1 characterized in that the at least one reactive dystuff is a compound of the formula formula (I)

Chromoph wherein the Chromophore is the radical of a monoazo dye of the formula

in which Ki is a radical of the benzene or naphthalene or benzochinone series or a heterocyclic radical and (R₃)_n and (R₄)_m are n = 0 to 3 and m = 0 to 6 identical or different substituents chosen from the group consisting of Ci -C₄ alkyl, Ci -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido, halogen, carboxyl and sulfo, or the Chromophore is the radical of a polyazo, metal complex azo, anthraquinone, formazan, phthalocyanine or dioxazine dye; Y is chlorine or fluorine; X is -NRiR₂ wherein, Ri is H; Cι_-6alkyl; substituted Cι_₆alkyl or C_1-6alkyl, which is interrupted by one or more atoms from the group consisting of O, N and S; R₂ is H; C_1-6alkyl; substituted C_1-6alkyl; Cι_-6alkyl, which is interrupted by one or more atoms from the group consisting of O, N and S or phenyl which is substituted by one or more carboxy, sulfo, or Ri and R₂ together with the nitrogen atom form a 5, 6 or 7 membered heterocyclic ring which optionally can contain more than one heteroatom from the group consisting of N, O and S and which may be additionally substituted by a Cι_-2alkyl-OH group; or salts thereof.

5 Process for producing a stable liquid formulations comprising at least one reactive dyestuff by adding the alkali polyacrylates or polymethacrylates and the 2-(2- Diethylaminoethoxy)ethanol and water, and, if necessarily, also further additives to a reaction mixture containing reactive dyestuffs, or filter-cake obtained by filtration continued on salting-out.

6. Use of liquid formulations according to claim 1 for printing or dyeing or ink- jet printing of hydroxy-group-containing or nitrogen-containing organic substrates.

7. Use of liquid formulations according to claim 6 for printing or dyeing or ink-jet printing of textile materials comprising cotton or paper or papery products or cardboard.

8. A Process for printing or dyeing or ink-jet printing of hydroxy-group-containing or nitrogen-containing organic substrates characterized in that a liquid formulation according to claim 1 is used.

9. Substrates printed or dyed or ink-jet printied by a process according to claim 8.