Textile matter absorbent coloured and its process of colouring.

The present invention relates to textile materials, in particular those of hydrophilic nature and especially cellulosic textile materials, as well as their immunostaining azo dyes.

According to the invention, the invention concerns a hydrophilic textile material dyed using a dye of formula:

where - d is the residue of a diazotizable tétrazotable or component;

. - ^ The R is a hydrogen atom or an alkyl radical, chlorine, acetamido, benzamido, carbamoyl or a carbamoyl radical substituted with nitrogen, e.g. - CONHBr or preferably a radical cayno;

* 2 - 9.ï is alkyl, especially methyl, optionally substituted with a chlorine atom,, a phenyl group, optionally substituted with an alkyl or alkoxy group, or a carboxylic acid group or carboxylic acid ester;

or R ^ - and Rj -, taken together with the carbon atoms in position 3 on the core 4 or the pyridone, may form an alicyclic ring or aromatic so that, for example, RJ45 ^ and R₂ may together form a tri - or tetramethylene forming with a pyridone penténo 00 C.]-pyrido-to-2-one or a hex çbj-pyrido-to-2 One, or alternatively R and R ^₂ can form with the adjacent ring carbon atoms the pyridone a benzene ring giving a benzo (jb3-pyrido-to-2 One;

- R is an aryl group carrying one or more sup -^J . 111 tituants for N0 - selected from₂'^_S0 2^R' "^C0R/ COOH,

FS - ^ - or NC (wherein R¹ is an optionally substituted alkyl or aryl group); and

- n is an integer that may be 1 or 2.

Preferred dyes are those deriving from the

the L - (2 'or 3' or 4' - nitrophenyl) - 3-cyano 4-methyl 6 hydroxy-a Py-to-rids itself 2 and one as a coupler.

It will be appreciated that the couplers and # therefore, the dyes used in the invention may exist in a number of tautomeric forms. For convenience, it only shows a single tautomeric form ^ but it is to be understood that the present memory relates the dyes under any one of the possible tautomeric forms.

The present invention can be used in any component diazotizable tétrazotable or suitable, especially those deriving from amides of the series of 1' anthraquinone and naphthalene and those derived from heterocyclic amines. However, are particularly useful constituents whereinD tétrazotables and diamine from the benzene series, such that d is preferably a radical phênyle which may be substituted with one or more chlorine or bromine and/or hydroxyl radicals, a cyano, a nitro, alkyl, in particular methyl and ethyl, trifluoromethyl, alkoxy, in particular methoxy and ethoxy, carboxylic acid ester, optionally substituted phênyle, aniline, benzamido, phenylazo or substituted phenylazo, especially methyl-phenylazo, nitro phenylazo ouanilinophénylazo, - or. D is a divalent radical from diamines of the series of benzene in which one of the amino groups can be attached to a substituent on the benzene ring.

As specific examples of amines suitable of the benzene series, is that 3.5-trifluoromethyl-aniline derivatives, the 2-trifluoromethyl-4 a-chloraniline, the 2 a-chloraniline, the 3 a-chloraniline, the 2.5-to-dichloraniline, the 2-nitrate 4-methoxyaniline, the 2-methoxy-5-chloro-aniline, the 2.5-to-dimêthoxy-a 4 a-cyananiline, the ester beta 'ethoxy ethyl p-aminobenzoic acid, the 2-methoxy-4 a-benzamido-to-5-methylaniline, the 2.5-to-dimé-to-thoxy-a 4 a-benzamido-aniline derivatives, the 2.5-diethoxy-a 4 a-benzamido-aniline derivatives, the 3 a-roéthoxy-to-4-amino diphênylaraine, ià 2.2'-dimethyl-4.4 ' a-diamino diphenylamine, the 4-methoxy-4¹ - amino diphenylamine, the 3-me-to-polyethylene resins and 4 - (3¹¹ - methyl-phenylazo) - aniline derivatives, the 2.5-dimethoxy-a 4 - (4 '- nitrophenylazo) - aniline derivatives, the 2-methoxy-4 - (2'-nitrate 4 'a-Methylphenylazo) - 5-methylaniline # the 2 ethoxy 4 - (P--amino 4'-anilino phënylazo) - 5-methylaniline and sulfanilamide.

As specific examples of amines suitable for the series of 1¹ an anthraquinone, mentioned are, in particular, the 2 - 1-and amino anthraquinone.

The textiles with hydrophilic coloration of the azo dyes defined above may be in the form of a wick, wire or a woven or knit fabric.

Preferably, the are cellulosic textile materials as viscose rayon, which may be mixed with other types of materials, as soon hydrophobic plastics.

Conveniently the dyed textile materials forming the azo dyes in situ on the fiber.

Thus, according to another feature of the invention, it provides a method for dyeing textile materials hydrophilic textile materials or mixtures of hydrophilic and hydrophobic textile materials, wherein the fabric material is applied to an alkaline solution of a 6 hydroxy-pyrido and 2 and one of formula:

%

(where 1 - Χχ, CD 1 * 2 have meanings defined above; and

- R.₄ is a hydrogen atom or a carbamoyl group) and then coupling the diazotized compound with a pyridone or tétrazoté.

The pyridone and preferred components whereinD tétrazotables or preferred for use in the method are those already defined above.

Can be used in the method of the present invention any alkaline substance having a solubilizing effect on 1 'hydroxy-to-pyridone derivative as, for example of 1' sodium hydroxide, sodium carbonate or sodium acetate or potassium salts equivalents that will the soluble salt of alkali metal 1¹ hydroxy pyridone derivative.

The alkaline solution can be applied onto the textile material by any known technique, such as by "sizing" the material in the solution which also contains additives to facilitate the impregnation, as wetting agents for usual.

Optionally, drying the impregnated material before treating it with a solution, a suspension or paste ' of component which can be diazotized tétrazoté or salt form is stable as a complex with zinc chloride. If, for example, the material must be completely colored in a dental shade, drying may not be needed before the impregnated material is immersed in a solution of the compound or diazotized tétrazoté. However, if the material is to be printed in one or more shades using a diazotizable tétrazotable or compound paste, a pre-drying of this material is preferable.

In another aspect of the method, which is first transforming the constituent diaSsotable or tétrazotable in stable derivative such as compound diazoamino which can be applied onto the textile material in admixture with the coupler, the dye is then generated in situ on the material by a subsequent acid treatment or by steaming.

In another aspect of the method of the invention, applied pyridone in concert with sodium nitrite, the diazo compound or tetrazo and dye being generated in situ on the material by the application of the amine precursor acidified.

When the or pyrid-to-2 One has a carbamoyl group in position 5, the coupling reaction takes place more slowly than in the case of or pyrid-to-2 One corresponding wherein position 5 is unsubstituted, as would be expected based.

Finally, the material is dried and colored and is subjected to a cleaning treatment usually in water to be removed from the surface of the material or the unused pyridone optionally unincorporated dye that loosely adheres thereto.

Are obtainable pyridones for copulation by a number of method such as those described, for example, in "Heterocyclic compounds containing - pyridin 3 hand curves gives the ITS DNA" (heterocyclic compounds; pyridine and its derivatives;

third part) which was published by Klingsberg to editing Interscience Publishers on in 1962.

Typical methods, e.g. (1) the condensation of compounds of the formulae

R₂COCH₂ The R - COOalkyl CHgCOO alkyl and alkyl

in the presence of an excess of an amine of formula

R₃ THE NH -₂ ;

(ii) cyclising a glutaconamide disubstituted alpha-beta and corresponding to the formula:

R1

alkyl OOC.CH₂ C. C.CONHI=^

R2

which is obtained by condensing itself, in the presence of a basic catalyst, compounds of formulas

R₂COCH₂ COO-alkyl and R₁ HM₂CONHR₃ ;

(lll) or cyclization of a disubstituted glutaconamidealphabêta and having the formula

lii NKCOCH COO-alkyl c=c

^K 2

obtained itself or condensing compounds of formulas. The R çocochjconh, and COOalkyl EjCH alkyl.

They are prepared conveniently by the method described in British Patent n-®' 46360/75 deposited. 10 november 19 .75 by the applicant.•

Can be prepared of benzo [the Cj-pyrido-a 2 a-ones into condensing homophthalic anhydride. with an amine may be prepared and the penténo - or hex - fcj-pyrido-a 2 a-ones into faisantréagir of - the 2 a-carbétoxy thereof are cyclopentanone or - hexanone are, the cyanacétate ethyl amine and then by hydrolysis.

Prepared 5 carbamoyl-pyrido-a 2 a-ones into partially hydrolyzing the derivative 5 a-c.yano.

The constituents diazotized tétrazotés or for use in the invention can be easily obtained by conventional techniques known for the diazotization and the tétrazotatipn primary amines of the type defined above. Usually, the first forming a solution of the hydrochloride die the amine and added sodium nitrite in the presence of an excess of hydrochloric acid to low, temperature.

Generally, these constituents are unstable and are prepared immediately before use. However, they can stabilize as previously mentioned and, in fact, constituents or diazotized tétrazotés stabilized are available, in the form of powders on a commercial scale.

The invention provides a wide range of textile materials colored and, further, can be prepared a wide range of colored fabrics from a single copuiant serving as the pyridone. Thus, for example, when it is impregnated with a length of cloth together with the pyridone derivative selected, printing can then be diazotized with constituents or tétrazotés different, giving rise to various colors on the same length of fabric.

The method of the invention is particularly useful for dyeing mercerized cotton or non-mercerized or undergone caustic treatment and coloring the viscose rayon treated caustic or has not undergone such treatment. Obtainable with the pyridone by -

- erm as an electrode coupling yields high dyeing dyes, it is to say deep shades, tints.

The dyes of the invention can be used in concert with other dyes to give to broader shades of hue. For example, when dyed cellulosic materials, can be applied a precursor phthalocyanine type with component diazotë or tétrazoté, thereby changing the hue of the pyridone dye resulting.■

The ease with which a material is removed from:, after development, pyridone unused and the unfixed dye surface is particularly appealing, this quiqui.donne particularly good contrast between the regions - - printed and unprinted and very low levels of stain - on the unprinted areas or on the undertone.

Those skilled in this field will include that such a method may also be used over-printing a fabric already dyed or printed, obtain - prints having good undertone other than white.

It is to be appreciated that the use of this method for dyeing cellulose continuously in a single hue via appropriate amines, diazonium salts are stabilized or mixtures thereof with each other or mixtures of each.

The dyes of the invention teindront also hydrophobic materials, such as synthetic polyamide, cellulose triacetate and polyesters. Advantageously allows the dyes of the invention for dyeing of fabrics which are blends of hydrophilic materials and hydropho ' SES, for example fabric 50:50 or 67:33 or 80:20 of polyester/cotton.

May be performed 1-dyeing by any of the methods described above, except that after forming the dye on the fiber, colored material is dried and is subsequently subjected to treatment - of. fixing, for example heat setting by dry heat, steaming to ' elevated temperature or steaming under pressure to "fix" the-to-pigment on the hydrophobic fibers. The material is then subjected to a cleaning treatment with water is carried out in the normal way.

Thus, ' can be used one or more dyes of the present invention, generated from one or more pyridone, for dyeing or coloring both components of a cloth which is a mixture. Alternatively, you can use the dyes of the invention in combination with other dyes for most commonly has the dyeing hydrophobic materials and which may be other type of a pyridone azo dyes.

The invention is illustrated, but not limited, by the following example in which the parts and percentages are by weight.

The size of the mercerized cotton in a hot solution comprising 20 parts of 1 - (3'-nitrophenyl) - 3-cyano 4-methyl 6 hydroxy-pyrido-to-2 One, 20 parts of crystalline sodium acetate - and 1,000 parts of water, and then dried.

Alternatively, tetrasodium pyrophosphate is used instead of sodium acetate or dissolvable pyridone in caustic soda and then adding one equivalent of acetic acid to buffer the system, etet.l ' can then be padding cotton in the cold solution.

Prepared a printing paste of diazo or tetrazo from a mixture comprising 40 parts of the amines of diazotized or tétrazotée enumerated below and 500 parts of a paste to 3 percent "Indalca pa/1", which is a thickening agent type mannogalàctane obtained in Cesalpinia (SPAs, Italian) and which comprises 45 parts of acetic acid at 40 percent, that complete 1,000 parts by adding cold water.

After padding, the fabric material is printed using the printing paste, and then washed and dried. The color of the print obtained is shown below opposite the particular amine used for the preparation of the printing paste.

The amine. Color of the impres -

-•SiON is obtained 2 a-chloraniline yellow

1 - amino yellow anthraquinone gold 2.5 a-dimëthoxy-to-4-cyano aniline-orange/red

2 - methoxy-4 a-benzamido-to-5-methylaniline red

The impres•amino color_ sec ion is obtained

2.5 - diethoxy-4 a-benzamido-aniline is ruby/brown..

2.2^, - dimethyl-4.4^, - - diamino diphenylamine navy

2.5 - dimethoxy-4 - (4¹ - nitro phenylazo) -

aniline-brown