GB2115445A - Disperse dyeing of hydrophobic textiles - Google Patents

Abstract

A process for the colouration of hydrophobic fibres comprises applying disperse dyestuff of the formula: <IMAGE> where A = the radical of a diazotisable amine ANH2, X = NHR<2> or SR<3>, R<2>, R<3> and R<4> are each independently H or optionally substituted hydrocarbyl, and R and R<1> are each independently optionally substituted hydrocarbyl, or together with the nitrogen atom represent a heterocyclic ring and heating to effect fixation of the dyestuff. Process especially useful for polyester fibres. Many of the dyes of formula (1) are novel.

Description

SPECIFICATION Colouration and dyestuffs This invention relates to colouration and dyestuffs, in particular to colouration of hydrophobic e.g.

aromatic polyester fibres and dyestuffs for use in this field.

Colouring matters in the form of azo compounds derived from pyrimidine coupling components are well known and many have been proposed for the colouration of polyester fibres. Azo pyrimidine compounds have also been investigated for biological activity.

We have now found a particular class of pyrimidine dyestuffs of value in colouring hydrophobic fibres especially polyester fibres.

Thus according to the present invention there is provided a process for the colouration of hydrophobic fibres which comprises applying disperse dyestuff of the formula:

where A = the radical of a diazotisable amine ANH2, X= NHR2 or SR3, R2, R3 and R4 are each independently H or optionally substituted hydrocarbyl, and R and R1 are each independently optionally substituted hydrocarbyl, or together with the nitrogen atom represent a heterocyclic ring and heating to effect fixation of the dyestuff.

The term "hydrophobic fibres" means those fibres not having a substantial affinity for water and which are normally coloured by disperse dyestuffs. Typical of such fibres are synthetic polyamides such as nylon 6 and 66, cellulose acetates with various degrees of acetylation up to triacetate and aromatic polyesters particularly poly(ethylene terephthalate).

ANH2 may be any of the carbocyclic or heterocyclic amines conventionally used in disperse azo dyestuff manufacture. Numerous examples of such amines which are free from water solubilising substituents are known from the patent and other literature.

It is preferred that A is an optionally substituted phenyl radical free from water solubilising substituents especially one of the formula:

where m is O or 1 when m isO one of R5 may occupy the 4 position, n and p are each independently 0, 1 , 2 or 3, each of the n substituents R5 are independently selected from halogen, NO2, CN, CF3, C alkyl, C14 alkoxy, C14 acyl, C14 acylamino, C 1-4 alkoxycarbonyl, C14 alkylsulphonyl, H2N.SO2, C14 alkylaminosulphonyl, di(C,~4 alkyl)aminosulphonyl and aryloxysulphonyl, and each of the p substituents R6 are independently selected from the atoms and groups given for Rb.

The preferred aryloxysulphonyl groups are phenoxysulphonyl in which the phenyl radical is optionally substituted by 1-3 substituents selected from halogen, C14 alkyl or C14 alkoxy.

As examples of the amines ANH2 which may provide the radical A there may be mentioned aniline, 4-nitroaniline, 4-cyanoaniline, 4-methoxyaniline, 4-(methylthio)aniline, 4-(methylsulphonyl)aniline, 4 (methoxycarbonyl)aniline, 4-(ethoxycarbonyl)aniiine, 4-aminoacetophenone, 4-aminoazobenzene, 4aminobenzene sulphonamide, 4-aminobenzenesulphon-N-methylamide, 4-aminobenzenesulphon-N,Ndimethylamide, 4-thiocyanatoaniline, 4-bromoaniline, 4-chloroaniline, 4-phenoxysulphonylaniline, 4 (4'-methylphenoxy)suIphonylaniline, 4-(4'-chlorophenoxy)su Iphonylaniline, 4-(4' methoxyphenoxy)sulphonylaniline, 4-[(beta-ethoxy)ethoxycarbonyl]aniline, methyl 4 aminobenzenesulphonate, 4-aminobenz-N,N-diisopropylamide, 2,4-dinitroaniline, 2-chloro-4 nitroaniline, 2-cyano-4-nitroaniline, 2-methoxy-4-nitroaniline, 4-chloro-2-methoxyaniline, 3,4 dichloroaniline, 3,4-dicyanoaniline, 2,4-dichloroaniline, 2,4-dicyanoaniline, 2,6-dichloro-4-nitroaniline, 2-bromo-6-chloro-4-nitroaniline, 4-chloro-2-nitroaniline, 4-chloro-3-nitroaniline, 4-(ethoxycarbonyl) 2-nitroaniline, 2-chloro-4-ethylsulphonylaniline, 2-methylaminosulphonyl-4-nitroaniline, 4-ethyla minosulphonyl-2-nitroaniline, 2-(isopropoxycarbonyl)-4-nitroaniline, 4-nitro-2 trifluoromethylaniline, 2-ethoxycarbonyl-4-nitroaniline, 3,4-bis(methoxycarbonyl)aniline, 3-chloro-6-methyl-4-nitroaniline, 2-hydroxy-4-nitroaniline, 2-nitroaniline, 2-chloroaniline, 2-bromoaniline, 2-methoxycarbonylaniline, 2-ethoxycarbonylaniline, 2-cyanoaniline, 2methoxy-5-methylaniline, 2-cyano-3-methoxyaniline, 2,6-dicyanoaniline, 2-amino-6methoxybenzamide, 2-acetoxyaniline, 2-methyl-6-nitroaniline, 2-(n-butoxycarbonyl)aniline, 2,3bis(ethoxycarbonyl)aniline, 2-cya no4-methylaniline, 2-amino-6-ethoxybenzamide, 2-bromo-6-cyano4-nitroaniline, 2-amino-4,4'-dimethylazobenzene, 2-aminophenol, 4-amino-3-nitrodiphenyl, 5-chloro2-ethoxyaniline, 5-chloro-2-methoxyaniline, 3-nitroaniline, 2,4-dimethyl-5-nitroaniline, 3-chloro-2methylaniline, 5-ethoxy-2-methylaniline, 3,5-dimethoxyaniline, 3,5-dinitroaniline, 3-methoxy-5nitroaniline, 3-ethoxy-5-nitroaniline, 3,5-dichloroaniline, 4-methyl-3-nitroaniline, 3aminobenzenesulphonamide, 3-nitro-5-trifluoromethylaniline, 2,5-difluoroaniline, 3,5bis(methoxycarbonyl)aniline, 3,5-bis(aminosulphonyl)aniline, 2-bromo-5-nitroaniline, 5-bromo-2methylaniline, 3-trifluoromethylaniline, 3-amino-4-chloroacetophenone, 3-amino-4chlorobenzenesulphonamide, 2-chloro-5-cyandaniline, 2-chloro-5-ethoxycarbonylaniline, 2-chloro-4methyl-5-nitroaniline, 2,5-dichloro-4-methylaniline, 2,5-dichloroaniline, 4-chloro-3-methylaniline, 4chloro-2-methyl aniline, 2-aminothiazole, 2-amino-3,5-dinitrothiophene, 2-amino-3-ethoxycarbonyl-5nitrothiophene, 2,4-dicyanothiophene, 2-amino-6-thiocyanatobenzthiazole and 2-amino-6methoxybenzthiazole.

The groups R, R', R2, R3 and R4 may include various optionally substituted aryl, aralkyl and alkyl groups. Preferred groups are phenyl, benzyl and phenyl ethyl in all of which the ring may carry 0 to 2 substituents each selected from halogen, NO2, C 1-4 alkyl especially CH3 and C14 alkoxy especially OCH3; together with the especially preferred groups which are C14 alkyl groups substituted by O to 2 atoms or groups each selected from halogen, especially Cl or Br, CN, OH, C1~4 alkoxy or 1-4 alkoxycarbonyl.

Preferred dyes include those in which one or both of R2 and R4 are H.

Specific examples of optionally substituted alkyl groups are methyl, ethyl n-propyl, isopropyl, nbutyl, beta-chloroethyl, beta-bromoethyl, gamma-chloro-beta-hydroxypropyl, beta-cyanoethyl, betahydroxyethyl, beta-methoxyethyl, beta-ethoxyethyl, methoxycarbonylmethyl and (betamethoxycarbonyl)ethyl.

Further examples of the groups R, R', R2, R3 and R4 will be apparent from the pyrimidine compounds named later to illustrate those suitable for preparing dyestuffs of formula (1).

Preferred dyes for use in the process of the invention have one or more of the preferred forms given above for A, R, R', R2, R3 and R4.

The dyestuff may be applied to the hydrophobic fibres in the form of an aqueous dispersion which may be prepared by conventional methods, for example, by milling the dyestuff with water and a suitable dispersing agent such as the sodium salt of a naphthalene-2-sulphonic acid/formaldehyde condensate.

The dyestuff may be applied to the hydrophobic firbres in a loose form or when converted into yarns, threads or woven or knitted textile materials. The various hydrophobic fibres may be present as blends with other types of fibres e.g. aromatic polyester and cellulose fibres such as cotton.

The above-defined colouration process may conveniently be carried out by immersing the fibres in whatever form in an aqueous dyebath containing one or more of the said dyestuffs, which dyebath preferably contains a non-ionic, cationic or anionic surface-active agent, or a cationic or anionic surfaceactive agent together with a non-ionic surface active agent, and thereafter heating the dyebath for a period at a suitable temperature. The dyeing process can either be carried out at a temperature between 90 and 1 000C, preferably in the presence of a carrier such as biphenyl or o-hydroxybiphenyl, or at a temperature above 1 00 C, preferably at a temperature between 1200 and 1400 C, under superatmospheric pressure.

Alternatively, the aqueous dispersion of the dyestuff can be applied to the fibres in fabricated textile materials by a padding or printing process, followed by heating at temperatures up to 2300 C, or by steaming of the textile material. In such processes it is preferred to incorporate a thickening agent, such as gum tragacanth, gum arabic or sodium alginate, into the aqueous dispersion of the said dyestuff.

At the conclusion of the colouring process it is preferred to give the coloured fibres a "reduction clear" treatment in a warm, dilute aqueous alkaline solution of sodium hydrosulphite in order to remove any unfixed azo dyestuff from the surface of the fibres. In the case of those dyestuffs which are soluble in aqueous alkali or which contain at least one group which is converted into a water-solubilising group by the action of aqueous alkali, the treatment with sodium hydrosulphite may be omitted, a simple treatment with warm dilute aqueous alkali free from reducing agent being sufficient to remove unfixed dyestuff.

The dyestuffs may also be applied to textile materials by known methods of transfer colour printing such as sublimation transfer printing, optionally under reduced pressure, and wet transfer printing.

The dyestuffs also find application for the melt colouration of polymers such as aromatic polyesters, and can also be used as pigments for the colouration of inks and paints, such dyestuffs being incorporated in known manner into conventional ink or paint formulations.

Many of the dyestuffs defined above by formula (1) are novel compounds and are a further feature of the present invention. Thus a further feature of the invention are dyestuffs of formula (1) as defined above providing that A is not 4-chlorophneyl.

A preferred class of novel dyes are as defined above as preferred for use in the process of the invention with the proviso that A as defined by formula (2) does not include 4-chlorophenyl.

It will be appreciated that the present invention also includes processes for the colouration of hydrophobic fibres with the novel dyestuffs given above and with the dyestuffs of formula (1) in which A is 4-chlorophenyl.

The invention further provides a process for the manufacture of the dyestuffs of formula (1) which comprises coupling the diazonium salt from an amine of formula ANH2 with a pyrimidine coupling component of the formula:

where A, X, R, R' and R4 have the meanings given above.

The diazonium salt from the amine ANH2 may be obtained by diazotisation of amine ANH2.

The diazotisation and coupling may be carried out by known methods for these reactions. For example, the diazotisation may be carried out by adding sodium nitrite to a solution or dispersion of the amine ANH2 in hydrochloric acid or aqueous sulphuric acid, or to a solution of the amine in concentrated sulphuric acid, or a mixture of concentrated sulphuric acid with an organic acid such as acetic acid and/or propionic acid, or by stirring the amine with nitrosylsulphuric acid, followed by addition of the resulting solution or dispersion of the diazonium compound to a solution of the coupling component in water or in a mixture of water and a water-miscible organic liquid, if necessary adjusting the pH of the mixture to facilitate the coupling reaction, and finally isolating the resulting dyestuff by conventional methods.

Usually diazotisations are carried out at temperatures below room temperature e.g. 0--100C and coupling at around room temperature e.g. 1 0-300C.

Examples of amines ANH2 are given above.

As examples of the pyrimidine coupling component of formula (3) there may be mentioned 2-N,N diethylamino-4,6-di(methylamino)pyrimidine; 2-N,N-diethylamino-4-ethylamino-6-methylamino pyrimidine; 2-N,N-diethylamino-4,6-di(2-hydroxyethylamino)pyrimidine; 2-N,N-diethylamino-4,6-di(3methoxypropylamino)pyrimidine; 4-amino-2-N,N-diethylamino-6-(2-hydroxyethylamino)pyrimidine; 4 butylamino-2-N,N-diethylam ino-6-(3-methoxypropyla mino)pyrimidine; 2-N,N-diethylamino-4-(2hydroxyethylamino)-6-(3-methoxypropylamino)pyrimidine; 2-N,N-diethylamino-4 ethoxycarbonylmethylamino-6-(2-hydroxyethylamino)pyrimidine; 2-N,N-dimethylamino-4,6 di(methylamino)pyrimidine; 4-amino-2-N,N-dimethylamino-6-(3-methoxypropylamino)pyrimidine; 2 N,N-dibutylamino-4,6-di(2-hydroxyethylamino)pyrimidine; 4-amino-2-N,N-di(3-methoxypropylamino)6-methylamino pyrimidine; 4-amino-2-N,N-di(2-hydroxyethylamino)-6-methylamino pyrimidine; 4 amino-2-N,N-di(2-hydroxyethylamino)-6-(3-methoxypropylamino)pyrimidine; 4-butylamino-2-N,N methyl-N-phenylamino-6-(2-hydroxyethylamino)pyrimidine; 2-N,N-diethylamino-4,6di(phenylamino)pyrimidine; 4-amino-2-N,N-diethylamino-6-ethylthio pyrimidine.

These pyrimidine coupling components can be obtained by various methods for example a di(optionally substituted hydrocarbyl)guanidine may be reacted with an ester of malonic acid to give a 2-N,N-di(optionally substituted hydrocarbyl) amino-4,6-dihydroxypyrimidine which is then converted to the 4,6-dichloro compound e.g. by reaction with phosphorus oxychloride, and finally reacted with ammonia, a primary amine, a metal hydrosulphide or a thiol. The reaction takes place stepwise so different substituents may be introduced into the 4- and 6- positions if desired.

Alternatively 2,4,6-trichloropyrimidine, obtained by chlorinating barbituric acid may be reacted with a secondary amine to obtain the 2-N,N-di(optionally substituted hydrocarbyl)amino-4,6dichloropyrimidine. However this is usually mixed with the isomeric product with the amino group in the 4-position making a purification essential to obtain the dyes of the invention free from unwanted products.

There is also provided a second process for the manufacture of dyestuffs of formula (1) which comprises reacting a dyestuff of the formula:

wherein A, R, R' and R4 have the meanings given above, and hal is a halogen usually chlorine, with ammonia, a primary amine, a metal hydrosulphide or a thiol.

This second process is usually carried out by dissolving or suspending the dyestuff of fromula (4) in a medium containing ammonia, primary amine, hydrosulphide or thiol and heating usually at 20 to 1000C.

Often it is desirable to have present a basic material to neutralise the liberated hydrogen halide and this can be an excess of reactant when this is ammonia or a primary amine.

Dyestuffs of formula (4) for use in the second process of the invention may be obtained by coupling the diazonium salt from amine ANH2 with a pyrimidine coupling component of the formula:

Examples of such dyestuffs include 2-N,N-diethylamino-4-methylamino-6-chloro-5-(4nitrophenylazo) pyrimidine; 2-N ,N-diethylamino-4-ethylamino-6-chloro-5-(2-cyano-4- nitrophenylazo)pyrimidine; 2-N,N-diethylamino-4-(2-hydroxyethylamino)-6-chloro-5-(2-chloro-4- nitrophenylazo) pyrimidine; 4-amino-2-N,N-diethylamino-6-chloro-5-(4-phenylazophenylazo) pyrimidine; 4-butylamino-2-N,N-diethyl-6-chloro-5-(4-nitrophenylazo) pyrimidine; 2-N,N-diethylamino 4-(2-hydroxyethylamino)-6-chloro-5-(2,4-dinitrophenylazo) pyrimidine; 4-amino-2-N,N-diethylamino6-chloro-5-(4-nitrophenylazo) pyrimidine.

As examples of the primary amines for use in the second process there may be mentioned methylamine, ethylamine, n- and iso-propylamine, n-butylamine, ethanolamine, 2-cyanoethylamine, 3- methoxypropylamine, aniline, o-, m- and p-toluidene, o-, m- and p-anisidine.

As examples of thiols for use in the second process of the invention there may be mentioned methylthiol, ethylthiol, n- and iso-propythiol, n-butylthiol and thiophenol.

A convenient metal hydrosulphide for use in the second process of the invention is sodium hydrosulphide.

The dyestuffs of the present invention and fibres coloured with them are characterised by high strength, good build-up to deep shades and good light fastness which is often much superior to closely related dyes.

The invention is illustrated by the following examples.

EXAMPLE 1 2-chloro-4-nitroaniline (1.73 g) suspended in 2N HCI (10 g) and water (35 g) at 0--50C was diazotised by the addition of 5N aqueous sodium nitrite solution (1.2 g).

2-N,N-diethylamino-4,6-di(2-hydroxyethylamino) pyrimidine (2.9 g) was dissolved in acetone (20 g) and the solution was added to water (50 g) stirring at 0--5 OC. The suspension of diazotised 2 chloro-4-nitroaniline was added to the pyrimidine solution at 0--5 OC and the pH of the mixture was adjusted to 4 by the addition of sodium acetate crystals. The mixture was stirred at 0--5 OC for 10 hours and the precipitated dyestuff was collected, dried and crystallised from n-butanol. The dyestuff has Amax (CHCI3) 500 nm, Emax 45,800.

When applied to aromatic polyester textile material from an aqueous dispersion a bright scarlet shade was obtained having excellent fastness to washing, light and changes of pH.

EXAMPLE 2 A mixture of 6-chloro-2-N,N-diethyla mino-4-(2-hydroxyethylamino)-5-(2-cyano-4- nityrophenylazo) pyrimidine (1 g), mono ethanolamine (1 g) and methylated spirits 740P (60 g) was stirred under reflux for 0.25 hours, cooled to room temperature and the product was then filtered off and dried.

The dyestuff had Amax (CHCl3) 510 nm, Emax 54,400.

When applied to aromatic polyester textile material from an aqueous dispersion a bright scarlet shade was obtained having excellent fastness to washing, light and changes of pH.

EXAMPLES 3-1 7 The following dyestuffs were obtained by diazotising in a known manner the amine given in the second column of the table and coupling the resulting diazonium compound with the coupling component given in the third column of the table, using essentially the method described in Example 1.

Most of the dyestuffs can also be prepared using the method described in Example 2, i.e. the reaction of chlorodiaminoazo pyrimidines with amines.

The shade obtained when each dyestuff was applied to aromatic polyester textile material is given in the fourth column and the Amax and zmax values of each dyestuff (may in parentheses) are listed in the final column.

TABLE I

#max (nm) Example Amine Coupling Component Shade (# max) 3 4-nitroaniline 2-N,N-diethylamino-4,6di(methylamino)pyrimidine Orange 488 (42,600) 4 2-chloro-4-nitroaniline " Scarlet 506 (39,700) 5 2-chloro-4,6-dinitroaniline " Red 510 (55,900) 6 4-aminoazobenzene " Scarlet 496 (40,400) 7 2-amino-3,5-dinitrothiophene " Violet 568 (52,600) 8 4-nitroaniline 2-N,N-diethylamino-4-amino6-thioethylpyrimidine Orange 461 (33,000) 9 " 4,6-diamino-2-N,N-dimethylaminopyrimidine " 458 (37,000) 10 " 2-N,N-diethylamino-4-(2-hydroxyethylamino)-8-(3-methoxypropylamino) pyrimidine " 486 (41,500) 11 2-chloro-4-nitroaniline " Scarlet 502 (45,100) 12 2-cyano-4-nitroaniline " " 518 (51,000) 13 2-chloro-6-cyano-4-nitroaniline " Red 530 (64,500) 14 2,4-dinitroaniline " " 524 (47,600) 15 2-bromo-4,6-dinitroaniline " " 16 4-nitroaniline 2-N,N-di(2-hydroxyethylamino)-4methylamino-6-(3-methoxypropylamino) pyrimidine Orange 482 (50,000) TABLE I-(continued)

#max (nm) Example Amine Coupling Component Shade (# max) 17 2-cyano-4-nitroaniline 4-amino-2-N,N-diethylamino-6-(2hydroxyethylamino)pyrimidine Scarlet 504 (46,000) 18 " 2-N,N-diethylamino-4-(2-hydroxyethylamino)-6-phenylaminopyrimidine Red 516 (55,000) 19 " 4-amino-2N,N-diethylamino-6phenylaminopyrimidine Scarlet 517 (47,000) 20 " 4,6-diamino-2-N,N-diethyl aminopyrimidine " 503 (52,900) 21 " 4-benzylamono-2-N,N-diethylamino6-(2-hydroxyethylamino)pyrimidine " 513 (47,600) 22 " 2-N,N-diethylamino-4-(2-hydroxyethylamino)-6-(4-methylphenylamino) pyrimidine Red 522 (50,000) 23 2-amino-5-nitrothiazole 2-N,N-diethylamino-4-(2-hydroxyethylamino)-6-(3-methoxypropylamino) pyrimidine Bluish-red 530 (45,000) 24 4-(4-nitrophenylazo)aniline " Violet 531 (44,000) 25 4-(2-chloro-4-nitrophenylazo) " Blue 546 (38,000) aniline 26 4-nitroaniline 4,6-diamino-2-N,N-diethylaminopyrimidine Orange 470 (52,400) 27 2-bromo-6-cyano-4-nitroaniline " Red 524 (57,000) TABLE I-(continued)

#max (nm) Example Amine Coupling Component Shade (# max) 28 2-chloro-4-nitroaniline 2-N,N-diethylamino-4-(3-methoxypropylamino)-6-phenylaminopyrimidine " 514 (47,800) 29 4-nitroaniline " Orange 498 (44,800) 30 2-bromo-6-cyano-4-nitroaniline 4-amino-2-N,N-diethylamino-6 (3-methoxypropylamino)pyrimidine Red 527 (64,000) 31 2-bromo-4,6-dinitroaniline " " 515 (53,900) 32 2-amino-6-chlorobenzthiazole 2-N,N-diethylamino-4,6-di(2hydroxyethylamino) pyrimidine Orange 478 (43,800)

Claims (1)

1. CLAIM

   1. A process for the colouration of hydrophobic fibres which comprises applying disperse dyestuff of the formula:

   where A = the radical of a diazotisable amine ANY2, X = NHR2 or SR3, R2, R3 and R4 are each independently H or optionally substituted hydrocarbyl, and R and R' are each independently optionally substituted hydrocarbyl, or together with the nitrogen atom represent a heterocyclic ring and heating to effect fixation of the dyestuff.