WO1997036961A1

WO1997036961A1 - Reactive dyes

Info

Publication number: WO1997036961A1
Application number: PCT/GB1997/000707
Authority: WO
Inventors: Andrew Hunter Morris Renfrew
Original assignee: BASF SE; Zeneca Ltd
Current assignee: BASF SE; Syngenta Ltd
Priority date: 1996-04-02
Filing date: 1997-03-14
Publication date: 1997-10-09
Anticipated expiration: 1998-10-02
Also published as: ID16502A; GB9606933D0; JP2000508012A; AU1934997A

Abstract

A dye having at least two groups each of which independently is of formula (1) and salts thereof, wherein: A is a halo triazinylamino reactive group; L1 is an arylene group; R?1 and R2¿ are each independently H or alkyl; Q is a group of the formula -CO- or -SO¿2?-; and B is an optionally substituted vinyl group or a group which is converted into an optionally substituted vinyl group in the presence of aqueous alkali.

Description

Reactive dyes

This invention relates to reactive dyes, their preparation and use for the coloration of materials and to materials when coloured by the dyes.

According to the present invention there is provided a dye having at least two groups each of which independently is of the formula (1):

R¹ R2

— A— N— L¹-N— Q— B (1) wherein:

A is a halo triazinylamino reactive group; L¹ is an aryiene group;

R¹ and R² are each independently H or alkyl; Q is a group of the formula -CO- or -S0₂-; and

B is an optionally substituted vinyl group or a group which is converted into an optionally substituted vinyl group in the presence of aqueous alkali. It is preferred that each group of formula (1) is attached to a carbon atom in an aromatic ring of the dye, for example a phenylene or naphthalene ring.

Preferred dyes according to the invention contain at least one, more preferably at least 3 and preferably less than 11 sulpho groups.

The halo triazinylamino reactive group is preferably a 2,4,6,-5-triazinylamino group carrying a Cl or F atom, preferably a Cl atom.

The aryiene group L¹ is preferably a mono- or dicyclic aryiene group. The preferred aryiene groups are optionally substituted phenylene and optionally substituted naphthylene. The optional substituents which may be present on L¹ are preferably independently selected from halo, especially chloro; alkoxy, especially C_1-6 alkoxy; alkyl, especially C_1-6 alkyl; sulpho; carboxy; and hydroxy.

It is preferred that R¹ and R² are each independently H or C_1-4 alkyl, more preferably H or methyl, especially H.

It is preferred that Q is a group of the formula -CO-. B is preferably a group of the formula (2) or (3):

— C =C . (2)

-R^£

R³ R⁴ I I -C H-C H Y (3) wherein:

R³, R⁴ and R⁵ are each independently H, halo or alkyl; and

Y is -OSO₃H, -SSO₃H, halo or -OCOCH₃.

When R³, R⁴ or R⁵ is halo it is preferably Cl or Br. When R³, R⁴ or R⁵ alkyl it is preferably C^-alkyl, especially methyl and ethyl.

It is preferred that R³ is H, methyl, ethyl, Cl or Br. More preferably R³ is H, methyl or Cl. It is especially preferred that R³ is H.

Preferably R⁴ and R⁵ each independently is H or C_1-4-alkyl, more preferably H or methyl. It is especially preferred that R⁴ and R⁵ are H. Preferably Y is -OS0₃H; -SS0₃H; Cl or Br, especially Cl; or -OCOCH₃; more preferably Y is -OS0₃H or Cl.

In light of the foregoing preferences, the group of Formula (1) is preferably of the Formula (4):

wherein:

W is halo;

M is one of the optional substituents described above for L¹ ;

R⁶ is H or alkyl; and R¹, R² and B are as hereinbefore defined.

W is preferably Cl or F.

Preferably M is Cl, methoxy, methyl, sulpho or carboxy, more preferably sulpho or methyl.

R⁶ is preferably H or C_1-6-alkyl, more preferably H or methyl, especially H. The dye according to the invention is preferably a water-soluble azo, anthraquinone, phthalocyanine, triphenodioxazine or formazan dye. Thus preferred dyes of the present invention are of the formula D-(T)_n wherein: each T independently is a group of the Formula (1), preferably of Formula (4), as hereinbefore defined; n is > 2; and

D is the residue of an azo, anthraquinone, phthalocyanine, triphenodioxazine or formazan chromophore. Examples of groups represented by D are given in the following pages in Formulae (5) to (12) wherein D is the portion of the illustrated molecules other than the groups represented by T.

Preferred azo dyes of the invention are monoazo and disazo dyes. Preferred monoazo dyes are of the formula T-L²-N=N-L³-T wherein L² and L³ are optionally substituted aryiene, heteroarylene or stilbene groups and each T independently is as hereinbefore defined. It is preferred that each aryiene group independently is a mono- or di-cyclic aryiene group. Preferred aryiene groups are optionally substituted phenylene and optionally substituted naphthylene. Preferred heteroarylene groups are pyridonylene and pyrazolonylene.

A first preferred monoazo dye is of the Formula (5) or salt thereof:

wherein:

X is H or sulpho; each T and L² independently is as hereinbefore defined. L² is preferably optionally substituted phenylene or naphthylene, especially a phenylene or naphthylene group having at least one sulpho substituent. Further optional substituents which may be present on L² include a halogen atom, especially chlorine; an alkyl group, especially C_1-4-alkyl, more especially methyl; an acylamino group, especially acetyiamino, benzamidσ or sulphonated benzamido; amino; hydroxy; and an alkoxy group, especially C_1-4-alkoxy, more especially methoxy. L² preferably has from one to three of said substituents.

As examples of phenylene groups having at least one sulpho substituent there may be mentioned 2-sulphophenylene; 2-sulpho-4-nitro-1,3-phenylene; 2-sulpho-5-nitro- 1 ,4-phenylene; 4-sulpho-2-methyl-1 ,3-phenylene; 5-sulpho-2-methyl-1 ,4'-phenylene; 2- sulpho~4-methyl-1 ,3-phenylene; 5-sulpho-2-methoxy-1,3-pheπylene; 2-sulpho-4- methoxy-1 ,3-phenylene; 4-sulpho-2-chloro-1 ,3-phenylene; 5-sulpho-2-carboxy-1 ,3- phenylene; 2,4-disulpho-1 ,3-phenylene; 2,5-disulpho-1,3-phenylene; and 3,5-disulpho- 1 ,4-phenylene.

As examples of naphthylene groups having at least one sulpho substituent there may be mentioned 1-sulpho-2,7-naphthylene; 1,5,7-trisulpho-2,8-naphthylene; 5,7- ^" disulpho-2,8-naphthylene; 6-sulpho-3,7-naphthylene; 4-, 5-, 6-, or 7-sulpho-8,3- naphthylene; 7-sulpho-1-hydroxy-4-amino-5,8-naphthyleπe; 4,8-disulpho-1 ,6- naphthylene; 3,8-disulpho-4,7-naphthylene; 3,6-disulpho-1-hydroxy-8-amino-2,7- naphthylene; 2,5,8-trisulpho-1,7-naphthylene; and 3,5,7-trisulpho-4,8-naphthylene. In dyes of Formula (5), T is preferably at the 6-, 7- or 8-position, especially the 6- or 8- position. When T is at the 8-position, it is preferred that X is a sulpho group at the 5- or 6- position.

A second preferred monoazo dye is of the Formula (6) or a salt thereof:

(6) wherein: each T and X independently is as hereinbefore defined.

A third preferred monoazo dye is of the Formula (7) or salt thereof:

wherein:

Ph is an optionally substituted phenylene group, especially sulphophenylene;

R⁷ is CN, CH₃ or carboxy; and

X and each T independently are as hereinbefore defined.

A preferred disazo dye is of Formula (8) or salt thereof:

T-L⁴-N=N-L -N=N-L⁶-T (8) wherein:

L⁴, L⁵ and L⁶ are each independently optionally substituted phenylene or naphthylene; and each T independently is as hereinbefore defined.

It is preferred that L⁵ is optionally substituted naphthylene and L⁴ and L⁶ are optionally substituted phenylene. The optional substituents which may be present on L⁴, L⁵ or L⁶ are preferably independently selected from halo, especially chloro; alkoxy, especially C^-alkoxy; C^-alkyl, especially methyl; sulpho; carboxy; hydroxy; amino; acylamino especially as acetamido, benzamido and sulphonated benzamido, and pyrimidinylamino or triazinylamino cellulose-reactive groups. As examples of groups represented by L⁴, L⁵ and L⁶ there may be mentioned phenylene, ureidophenylene and the aforementioned phenylene and naphthylene groups which have at least one sulpho substituent.

A preferred anthraquinone dye is of the Formula (9):

wherein the anthraquinone nucleus optionally contains a sulphonic acid group in the 5-, 6- or 7-, position; each V independently is a divalent organic linking group, preferably of the benzene series; and each T independently is as hereinbefore defined.

Each V independently is preferably a phenylene, diphenylene, 4,4'-divalent stilbene or azobenzene, optionally sulphonated. It is preferred that V contains one sulphonic acid group for each benzene ring present therein. A preferred phthalocyanine dye is of the Formula (10):

wherein: Pc is a metallo-phthalocyanine nucleus, preferably copper or nickel phthalocyanine; each R¹ is as hereinbefore defined; each G independently is a hydroxy or a substituted or unsubstituted amine group;

V¹ is a divalent organic linking group, preferably a C_1-4-alkylene or phenylene linking group; b > 2; and a is 0, 1 or 2; provided that a + b is not greater than 4.

A preferred triphenodioxazine dye is of the Formula (11) or a salt thereof :

(11) wherein : each V² independently is a divalent linking group, especially, C₂-₄-alkylene, phenylene or sulphophenylene;

Z¹ and Z² are halo, C_1-4-alkyl, or C^-alkoxy; and each X and T independently as hereinbefore defined.

Each V² independently is preferably -C₂H₄- or -C₃H₆-, X is preferably SO₃H, and each Z¹ and Z² independently are preferably Cl, methyl or ethyl, especially Cl or methyl.

A preferred formazan dye is of the Formula (12) or a salt thereof :

wherein :

X¹ is H, S0₃H or Cl; m and p each independently have a value of 0, 1 or 2; and each T independently is as hereinbefore defined; provided that the formazan group has at least one, and preferably at least two, sulpho groups.

It is preferred that m and p each have a value of 1.

Dyes according to the invention may be prepared by condensation of a dye having at least two dihalotriazinylamino groups with a compound of the Formula (13): H-N— L¹— N— Q-B ₍₁₃) R¹ R² wherein: R¹, R², L¹, Q and B are as hereinbefore defined.

The condensation is preferably carried out at 0°-80°C, especially 0°-50°C, more especially at 0°-40°C. The condensation is preferably performed in the presence of an acid-binding agent. The function of the acid-binding agent is to neutralise the hydrogen- halo acid as it is formed during the condensation. Accordingly any acid-binding agent may be used provided that it is not present in such a concentration that it causes hydrolysis of the reactants or causes some other undesirable side-reaction. It is preferred to use an alkali metal hydroxide, carbonate or bicarbonate, preferably added at such a rate that the pH of the mixture stays within the range 6.0 to 7.0 during the condensation. Dyes having at least two dihalotriazinylamino groups can be prepared by condensing a dye having at least two nucleophilic groups (e.g. amino groups) with a cyanuric halide.

The compounds of Formula (13) can be prepared by reaction of an amine of the formula (14) with a compound of the formula (15):

H — N — L ¹ — N - -H

(14)

B — Q — U (15) wherein:

R¹, R²,

Q and B are as hereinbefore defined; and

U is halo.

The compound of formula (13) may also be prepared by reaction of the compound (15) with an amine containing a nitro compound of the formula (16):

NO₂— L¹— N— H (16) R² followed by reduction of the nitro group, preferably using a suitable reducing agent such as iron or sodium sulphide. The amine produced may then be condensed with a compound of formula R¹^ wherein R¹ and U are as hereinbefore defined to give the desired compound (13). The dyes according to the present invention may also be prepared by condensation of a compound of formula (13) with a cyanuric halide. The resultant dihaiotriazinyl compound is then condensed with a dye having at least two nucleophilic groups.

Although dye formulae have been shown in the form of their free acid in this specification, the invention includes the dyes in their salt form, particularly their salts with alkali metals such as the sodium, lithium or mixed sodium/lithium salt.

The present invention also provides a process for the coloration of a substrate comprising applying thereto a dye according to the present invention, preferably in aqueous solution.

The reactive dyes of the present invention are suitable for colouring natural and artificial textile materials containing amino or hydroxyl groups, for example textile materials such as wool, silk, polyamides and modified polyacrylonitrile fibres, and more especially cotton, viscose rayon and other regenerated celluiosic materials. For this purpose the dyes can be applied to the textile materials by exhaust dyeing, or by padding or by printing using printing pastes containing the conventional thickening agents or oil-in- water emulsions, whereby the textile materials are coloured bright shades and possess good fastness to light and to wet treatments such as washing and also possess good wash off.

When applied under conventional reactive exhaust dyeing conditions the dyes give high fixation yields. Fixation yields of around 95% can be achieved even at relatively high dye on fibre concentrations, e.g. 5% by weight on weight. Such values are unusually high. As a consequence there is relatively little dye to remove during wash-off and the dyes are economical in use.

The new dyes are particularly valuable for colouring celluiosic textile materials.

For this purpose the dyes are preferably applied to the celluiosic textile material in conjunction with a treatment with an acid-binding agent, for example, sodium bicarbonate, sodium carbonate, sodium metasilicate, trisodium phosphate or sodium hydroxide, which may be applied to the cellulose textile material before, during and after the application of the dye.

The new dyes can be applied to textile materials containing amine groups, such as wool and poiyamide textile materials, from a mildly alkaline, neutral or acid dyebath. The dyeing process can be carried out at a constant or substantially constant pH, that is to say the pH of the dyebath remains constant or substantially constant during the dyeing process, or if desired the pH of the dyebath can be altered at any stage of the dyeing process. The invention is illustrated but not limited by the following Examples in which all parts and percentages are by weight unless stated otherwise. Example 1

Preparation of:

Stage (a)

Preparation of 4-amino-3,6-bis-(5-amino-2-sulphophenylazo)-5-hydroxy- naphthalene-2,7-disulphonic acid.

3-nitroaniline-6-sulphonic acid was diazotised by adding the 3-nitroaniline-6- sulphonic acid to an aqueous solution of concentrated HCl and 2N sodium nitrite solution at a temperature of 0-5°C. The diazonium salt was then coupled with an equimolar quantity of 4-amino-5-hydroxy-naphthalene-2,7-disuiphonic acid under acidic conditions. The 4-amino-3-(5-nitro-2-sulphopheπylazo)-5-hydroxy-naphthalene-2,7-disulphonic acid so formed was then coupled with an equimolar quantity of the diazotised 3-nitroaniline-6- sulphonic acid under alkaline conditions. The resulting dinitro disazo compound was then reduced to the triamino disazo compound by heating at 40°C for 1-2 hours with an aqueous solution of sodium sulphide. The pH of the reaction mixture was adjusted to pH 3 and the dis azo dye was collected by filtration and washed with brine solution. SJage bi

Preparation of N -(3-amino-4-methylphenyl)acrylamide.

To a solution of 4-methyl-3-nitro-aniline (15.2g, 0.1 mol) in methylene chloride (300ml) was added acryloyl chloride (10g, 0.11 mol) and triethylamine (11.1g, 0.1 mol). The reaction mixture was then heated under reflux for 6 hours followed by filtration to remove triethylamine hydrochloride formed by the reaction. The reaction mixture was charged into water (500ml) and the organic layer was washed several times with water. The organic layer was then separated off and dried over magnesium sulphate. The methylene chloride was removed from the reaction mixture by distillation. Ethanol (250ml) and iron filings (10g) were then added to the reaction mixture, which was then heated under reflux for 4 hours. The reaction mixture was filtered and the product was isolated by evaporation to give a grey-green solid (7.3g). Stage (c)

To a solution of 4-amino-3,6-bis-(5-amiπo-2-sulfo-phenyl-azo)-5-hydroxy- naphthalene-2,7-disulphonic acid (11g, 8mmol) in water (250ml) at 0°-5°C was added a solution of cyanuric chloride (3.2g, 17.4mmol) in acetone (50ml), with stirring whilst maintaining the pH between 5.0 and 6.0 by the addition of 2N sodium carbonate solution.

The mixture was stirred for three hours and N-(3-amino-4-methyl-phenyl)- acrylamide (4.1g, 17.5mmol) was added and the reaction was stirred for a further two hours at ambient temperature, whilst maintaining the pH between 6.0 and 7.0.

Sodium chloride (50g) was then added and the mixture was stirred for a further two hours. The dye was then collected by filtration, washed with sodium chloride solution (5%) and dried to give the final product (13.55g, 88% solid content) as a dark blue solid. It had a λ max of 610nm (H₂0 at pH 7).

Dyeing The title dye was applied to cotton under exhaust dyeing conditions using sodium carbonate as alkali, at 80°C. At 5% dye on fibre a fixation of 95% was achieved giving a strong greenish-navy shade. After washing off, the dyeing gave good wet fastness.

Example 2

Preparation of:

Stage (a)

Preparation of:

To a solution of 4-amino-4'-nitrostilbene-2,2'-disulphonic acid (4.1g, 9.2mmol) and 2N sodium nitrite (5m!s, 10.1 mmol) in water (100ml) was added a stirred mixture of concentrated hydrochloric acid (2.3ml, 23.0mmoi) and ice (200g). The reaction mixture was then stirred for 2 hours whilst maintaining the temperature below 5°C. Any excess nitrous acid was then destroyed by the addition of sulphamic acid. A solution of 3-aminoacetanilide (2.5g, 9.2mmol) in water (100ml) was added to the reaction mixture, the pH was adjusted to 6.0 and after stirring for 2 hours at 0-5°C, the precipitated solid was isolated by filtration.

The filter cake was dissolved in water (200ml) and the solution was added dropwise to a solution of sodium sulphide nonahydrate (5.9g, 24.8mmol) in water (100ml) whilst maintaining the temperature below 20°C. After stirring for 90 minutes at ambient temperature the pH of the reaction mixture was adjusted to 3.0 and the solid was collected by filtration and washed with saturated brine solution.

Stage (p)

Preparation of:

A solution of 2,4-diaminobenzene sulphonic acid (19g, 0.1 mol) in water (300ml) was adjusted to pH8 and cooled to 0-5°C. To the solution was added acryloyl chloride (11.14g, 0.12mol) over 30 minutes whilst maintaining the pH at 8. After stirring for 12 hours sodium chloride (60g) was added and the precipitated product was isolated by filtration to give a mixture of mono and bis acryloylated diaminobenzene sulphonic acid (37g). A solution of cyanuric chloride (3.7g, 20.2mmol) in acetone (50ml) was precipitated by pouring onto ice (100g). A solution of the mono and bis acryloylated diamino benzene sulphonic acid (8.1g) in water (100ml) was adjusted to pH 6 and charged to the cyanuric chloride solution whilst maintaining the temperature below 5°C. After stirring for 60 minutes the mixture was screened. Stage c) To a suspension of the product of stage (a) (10g, 9.2mmol) in water (500ml) was added dropwise the solution from stage (b) whilst maintaining the pH between 6.0 and 7.0. The reaction mixture was then stirred for 20 hours at 40°C, pH 5.0. Sodium chloride (32.5g) was then added to the reaction mixture and the product of the reaction was filtered off, washed with 50% brine solution and dried. The title dye obtained was an orange powder (17.8g, 76% solid content). It had a λ max of 421nm (H_zO at pH 7). Dyeing

The dye was applied to cotton under exhaust dyeing conditions using sodium carbonate as an alkali at 30°C, to give a bright reddish-yellow dyeing of very high fixation of 92 %. After washing the dyed cotton had good wet fastness.

Claims

1. A dye having at least two groups each of which independently is of the formula (1) and salts thereof:

5

R¹ R²

I I

— A— N— L -N— Q— B (1) wherein:

A is a halo triazinylamino reactive group; 0 L¹ is an aryiene group;

R¹ and R² are each independently H or alkyl;

Q is a group of the formula -CO- or -S0₂-; and

B is an optionally substituted vinyl group or a group which is converted into an optionally substituted vinyl group in the presence of aqueous alkali. 5

2. A dye according to claim 1 wherein Q is a group of the formula -CO-.

3. A dye according to either of the previous claims wherein L¹ is optionally substituted phenylene or optionally substituted naphthylene. 0

4. A dye having at least two groups each of which independently is of the formula (4) and salts thereof:

o wherein:

W is halo;

M is halo, alkoxy, alkyl, sulpho, carboxy, or hydroxy;

R⁶ is H or alkyl; and

R¹, R² and B are as defined in claim 1. 5

5. A dye according to any one of the previous claims wherein B is a group of the formula (2): R3

I .R' — C =C . (2)

wherein:

R³, R⁴ and R⁵ are each independently H, halo or alkyl.

6. A dye according to any one of claims 1 to 4 wherein B is a group of the formula (3):

R³ R⁴ I I — C H-CH Y (3) wherein R³ and R⁴ are each independently H, halo or alkyl and Y is OS0₃H, SS0₃H, halo or -OCOCH₃

7. A dye according to claim 1 which is of formula D-(T)_n wherein each T independently is a group of formula (1) in claim 1 ; n > 2; and D is the residue of an azo, anthraquinone, phthalocyanine, triphendioxazine or formazan chromophore.

8. A process for the manufacture of a dye according to claim 1 comprising condensation of a dye having at least two dihalotriazinylamino groups with a compound of the Formula (13):

wherein: R¹, R², L¹, Q and B are as defined in claim 1.

9. A process for the colouration of a textile material comprising applying thereto a dye according to any one of claims 1 to 7.

10. A process according to claim 9 for colouring celluiosic textile materials wherein an aqueous solution of the dye is applied to the material which is also treated with an acid- binding agent before, during or after the application of the dye.

11. A textile material coloured by a dye according to any one of claims 1 to 7.

12. A textile material coloured by a process according to claim 9 or 10.