GB2151654A - Direct disazo dyes - Google Patents

Abstract

Disazo compounds which, in the free acid form, are represented by the formula (1), impart red hues to cellulosic fibres (esp. cotton) and blends thereof with polyester, acrylic or polyamide fibres or wool. <IMAGE> wherein X is H or SO3H, Y is a group of the formula (2): <IMAGE> (where R1 is H, CH3 or C2H5 and R2 and R3 are independently H, Cl, CH3, SO3H or COOH) and D is a group of the formula (3): <IMAGE> (wherein R4 and R5 are independently H, CH3 or OCH3, Z is CONH, NHCO, SO2CH2 or SO2NH and R6 and R7 are independently H, CH3 or Cl).

Description

SPECIFICATION Disazo compounds and process for dyeing using the same This invention relates to disazo compounds and a dyeing method using the same. More particularly, the invention is concerned with disazo compounds which, in the free acid form, are represented by the formula (1):

wherein Xis H or SOBH, Y is a group ofthe formula (2):

(wherein R1 is H, CH3 or C2H5, and R2and R3 are independently H, CI, CH3, SO3H or COOH) and D is a group oftheformula (3):

(wherein R4 and Rg are independently H, CH3 or OCH3, Z is CONH, NHCO, SO2CH2 or SO2NH or SO2NH and R6 and R7 are independently H, CH3 or Cl), and a process for dyeing cellulosic fibers with the disazo compounds.

Recently, blends of polyester and cellulosic fibers have come into extensive use as textile material. In dyeing these blends, a one-bath one-step dyeing method wherein a disperse dye and an ordinary direct dye are employed under acidic, high-temperature conditions commonly used in dyeing polyester fibers brings aboutvarioustroubles, for example, a sharp decrease in the dyeing affinity ofthe direct dye to the cellulosicfiber and failure of gaining uniformly dyed materials due to aggregation ofthe direct dye in the dye bath. The only alternative, therefore, has been to adopt a two-bath dyeing or a one-bath two-step dyeing method, though both of them are undesirable from the view point of saving energy and time. Of direct dyes, red ones are most likely to invite the above-mentioned troubles.Forthese reasons there has been a strong need for red direct dyes which would have good dyeing affinitiesto cellulosic fibers under severe dyeing conditions of an acidic bath and elevatedd temperature. The present inventors have intensively endeavored to develop a red direct dye which would be able to dye, in combination with disperse dyes, polyester fibericellulosic fiber, especially polyester fiber1cotton (T/C), blends satisfactorily, without the foregoing troubles, by the one-bath one-step dyeing method under the acid-bath, hightemperature dyeing conditions. We have found, as a result, that the compounds represented by the formula (1 ) have very desirable properties for use underthese dyeing conditions and have now perfected the present invention.The compounds of the formula (1 ) are characterized by not only their great adaptability to the one-bath one-step dyeing method of T/C blends but also their high ability of giving excellentfastnesses, especially, fastness to washing.

The compounds of the formula (1) can, of course, dye in a conventional way cellulosicfibers such as cotton, rayon and flax. They may also be used in combination with another class of dye for a one-bath one-step dyeing method of blended textile materials, such as acrylicfiber/cotton, polyamidefiber/cotton and wool/ cotton blends, to dye cotton in red hue selectively.

The inventioon will now be described in more detail.

The disazo compounds represented by the formula (1 ) are usually prepared in the following manner.

A cyanuric halide, for example, cyanuric bromide or cyanuricfluoride, preferably cyanuric chloride, and 2-amino-5-naphthol-i,7-disulfonicacid or 2-amino-5- naphthol-7-sulfonic acid are condensed together (primary condensation), and the resultant condensate is further condensed with 6-amino-1-toluene- sulfonyloxy-naphthalene-3-su Ironic acid (secondary condensation). The condensate thus obtained is coupled with diazotized o-anisidine-5-sulfonic acid (primary coupling). Then, a compound represented bytheformula (2)':

(wherein R1, R2 and R3 are as defined above) is condensed with the coupling product (tertiary condensation).

Next, following an addition of a copper-complexing accelerator, if necessary, a copper-complexing agent is added to copperize the condensate. With the further addition of caustic alkali to make the reaction solution strongly alkaline, the product is hydrolyzed to give a compound, in the free acid form, having the formula (4):

wherein X and Y are as defined above. The com- pound of the formula (4) may be separated in the usual manner by acid precipitation orsaiting-outand filtration so that the product is taken out as a cake.

Alternatively, it may be transferred in the form of a solution to the subsequent step.

The compound ofthe formula (4) is then coupled with a diazotized derivative of a compound represented by the formula (5) (secondary coupling):

(wherein R4 through R7 and Z are as defined above) to obtain a compound represented by the formula (1).

Examples ofthe compound represented bythe formula (2)', i.e. components subjected to tertiary condensation, are as follows:

wherein the sulfonic acid group is shown in the free acid form.

Examples of the compound represented by the formula (5) i.e. components subjected to secondary coupling are as follows:

The foregoing reactions ofthe primary, secondary and tertiary condensations, primary and secondary couplings, copper-complexing and hydrolysis may be performed by the usual methods. Desirable conditions for these reactions will now be given. For the primary condensation, a temperature of Oto 25"C and a pH of0.Sto of preferably atemperature of 5 to 15"C and a pH of 0.5two 1.5 are used.The secondary condensation is carried out at 30 to 70"C and pH 4to 7, preferably at 40 to 50"C and pH 4.0 to 4.5. The primary coupling with the secondary condensate is at O to 30and pH 6to 9, preferablyat 10to 15and pH7to 8.

Thetertiarycondensation is effected at 80 to 1000C and pH 2to 7, Dreferably at90 to 950C and pH 2to 3 (where a compound oftheformula (2)' has a sulfonic acid group) or pH 5to7 (where a compound of the formula (2)' is free from a sulfonic acid group). The copper-complexing reaction is conducted at 90 to 1 00 C using copper sulfate, copper acetate or copper chloride, preferably copper sulfate, as a coppercomplexing agent and also employing, if necessary, aqueous ammonia, monoethanolamine, diethanolamine, N-methylethanolamine orthe like as a coppercomplexing accelerator.The hydrolysis reaction is performed using caustic soda or caustic potash as a causticalkali to maintain the pH in a strongly alkaline side of over pH 13 at a temperature of 60 to 90"C, preferably 60 to 70 C. The conditions to be used for the secondary coupling are a temperature of 5 to 15"C and a pH of 9to 10.Atemperaturefordiazotizations of o-anisidine-5-sulfonic acid and a compound represented by the formula (5) is 1 0'C or below 10"C. Of the disazo compounds represented by the formula (1), more desirable compounds are as follows:

(wherein Y and Dare as defined above).

Particularly desirable compounds of the abovementioned compounds are as follows:

wherein R8 and Rg are independently H, CH3, Cl or SO3H and R10 and R11are independently H, CH3 or Cl.

The novel disazo compounds ofthe present invention are used for dyeing of cellulosic fibers by a well-known process of dip dyeing or by printing. They are also applicable to cellulosicfibers or blends of cellulosicfiberwith other fibers by adopting hightemperature dyeing, carrier dyeing or other methods with another class of dye. Underthese dyeing conditions, the compounds of the present invention can dye cellulosicfibers and cellulosicfiber componentofthe blend in red hue with excellent color fastness to washing.

The compounds ofthe present invention can be used singly or as a mixture oftwo or more ofthem, or in combination with a dye belonging to another class such as a disperse, basic and acid dye. Particularly noteworthy effect of this invention is the fact that, with good adaptability to high-temperature acidic dyeing conditions, they can be used with disperse dyesforpolyesterto dyeT/C blends byaone-bath one-step dyeing method, without presenting any technical difficulty in dyeing operation or impairing various fastnesses of the dyed materials. Using a one-bath one-step dyeing method, in place of a two-bath or one-bath two-step dyeing method conventionally used in the dyeing ofT/C blends brings about energy saving, process simplification and other merits, which are of very great economical advantage.

The present invention will now be illustrated in more detail by referring examples below, although it is to be understood that the invention is not limited thereto.Throughoutthe examplesthe parts are all by weight, and carboxyl and sulfonic acid groups are shown in the free acid form.

Example 1 To 30 parts of ice water containing 0.1 part of "Liponox NA" (a dispersant manufactured by Lion Fat & Oil Co.), 3.7 parts of cyanuric chloride were added over 10 min. A solution of 6.3 parts of 2-amino-5-naphthol-1 ,7-disulfonic acid in 40 parts of water, at pH 7.5, was added thereto over 20 min, and the whole mixture was stirred at 10 Cfor2 hrto effect primary condensation. The pH graduallyfell to a final value of 0.7. To the resulting solution was added at once a solution of 7.9 g of 6-amino-1-toluenesulfony- loxynaphthalene-3-sulfonicacid in 50 parts of water at pH 8.0. The liquid mixture was heated to 50C.

During this temperature rise the reactant solution was kept at pH 4.5 with an aqueous soda ash solution, and was stirred at the same temperature for 2 hrto effect secondary condensation. Separately, 4.1 parts of o-anisidine-5-sulfonic acid were suspended in 20 parts of water containing 0.1 part of "Liponox NA" and 2.3 parts of hydrochloric acid were added to the liquid suspension, and the mixture was cooled below O"C with ice. 1.5 parts of sodium nitrite (in an about 30% aqueous solution) were added dropwise to mixture over about 20 min, and the whole mixture was stirred at 1 OOC or below for 1 hr (diazotization).

Thereafter, excess nitrite ions were removed with sulfamic acid, and the diazotized solution was added at once to the solution containing the secondary condensate under cooling with ice to 1 0 C, and the mixture was rapidly neutralized to pH 7.0 with a 10% aqueous soda ash solution. The same temperature and pH were maintained for 1 hr. To the reactant solution thus obtained, 3.7 parts of aniline were added, and the mixture was neutralized with 10% aqueous hydrochloric acid solution to pH 5.0. The temperature was raised to 95"C and the mixture was allowed to react atthattemperature for 3 hr (tertiary condensation).Separately, 5.0 parts of copper sulfate were dissolved in 25 parts of hot water, and 10 parts of an aqueous ammonia solution were added to the solution. The resulting solution was added to the solution containing the tertiary condensate to effect a coppercomplexing at95 Cfor3 hr, and a reaction solution containing the following compound was obtained:

To this solution 12 parts ofa 48% aqueous caustic soda solution at 70"C were added, and the mixture was stirred to effect hydrolysis for 2 hratthe said temperature.

Following the conclusion of hydrolysis, the product was neutralized with 35% hydrochloric acid, salted out by the addition of about 75 parts of sodium chloride, and then filtered to obtain a compound oftheformula (7) (18 parts):

Following the addition of 9.9 parts of the compound (7) to 200 parts of hot water the pH was adjusted with 10% caustic soda solution to 11.0 for complete dissolution ofthe compound (7), and then 3.0 parts of soda ash were added thereto.

This solution was cooled to 1 0 C or below with ice. Separately, 2.9 parts of3-amino-4-methoxy- 2'-methyl-3'-chlorobenzanilide were suspended in 20 parts of water containing 6 parts of 35% hydrochloric acid. The resulting suspension was cooled with ice to below 0 C, and 0.75 part of sodium nitrite in the form of a 30% aqueous solution was added dropwise thereto over 5 min. The liquid suspension was treated at 1 0 C or belowfor 1 hr, and then excess nitrite ion was removed with sulfamic acid. This was added, at 1 5 C or below and while maintaining a pH range from 9to 10with a 10% aqueous soda ash solution, to the above solution over 10 min.After agitation was continued for 4 hr, the temperature was raised to 80"C, and filtration was done to obtain the following compound (22 parts):

This compound dissolved in water in red, and its Amax in a 20% aqueous pyridine solution was 532 nm. It dyed cotton in red hue with excellent fastness to washing.

Example 2 The same procedure as in Example 1 was repeated with the exception that the primary condensation was effect using 4.7 parts of 2-amino-5-naphthol-7-sulfonic acid in place of 2-amino-5-naphthol-1 7-disulfonic acid.

The following compound corresponding to thatoftheformula(7)inExamplel wasobtained (16 parts):

Using 9.1 parts of the compound of the formula (9) instead ofthe compound (7) of Example 1,the procedure ofthe preceding example was continued to obtain the following compound (25 parts):

This compound dissolved in water in purplish red,and itsAmax in a 20% aqueous pyridine solution was 534 nm. This product was used to dye celiulosic fibers in reddish purple shades with good fastness to washing.

Example3 The same procedure as in Example 1 was repeated till the secondary condensation reaction. Then, 4.2 parts of metanilic acid in a powder form were added to the solution containing the secondary condensate while taking care notto foam it, and the temperature ofthe mixture was raised to 950C. Next, the pH was adjusted to 2.0 with a 10% aqueous hydrochloric acid solution and the mixture was allowed to react at that temperaturefor3 hr (tertiary condensation).

Acopper-complexing and hydrolysis procedure as in Example 1 was carried outto obtain thefollowing compound which corresponded to thatoftheformula (7) in Example 1:

To 200 parts of hotwater10.7 partsofthe compound oftheformula (11) were added. The mixture was adjusted to pH 10.5 with a 10% aqueous caustic soda solution and completely dissolved, and 2.0 parts of soda ash were added thereto.Separately, 2.4 parts of 3-amino-4methoxybenzanilide were suspended in 20 parts of water containing 2.5 parts of 35% hydrochlor- ic acid and the suspended mixture was cooled with ice to 0 C,then 0.75 partofsodium nitrite in a 30% aqueous solution was added dropwise thereto overabout5 min, and the mixture was treated at 1 OOC or below for 1 hrto prepare a diazonium solution. This solution was added to the solution containing the compound ofthe formula (11) at 1S0C or belowand pH 9to 10. The mixed solution was stirred for4 hr and then filtration was doneto obtain the following compound (18 parts) (13):

This compound dissolved in water in red hue and its ajax in a 20% aqueous pyridine solution was 527 nm.

Compounds of the formula (14) were prepared by the same procedure as in Example 1.

Table 1 shows groups Y and D, and Amax (nm in aqueous 20% pyridinesolution) of compounds oftheformula (14) and the hues of cellulosic fiber dyed with these compounds.

Table 1

Plo imax | EXue pie 4 326 bluish red FEL bluish red 4 --HN 528 'conr-(Tj) 6 -NcooH 520 oc 7 ;Ne C33 537 reddish purple oc 8 sY&commat; > ECONE 526 bluish red 9 | -CB 512 yellowish tC}la red 'sQNH 10 --HNSOH 312 ScdR 11 ; myB 520 bluish red S03iI cH3 12 ~E,y+Ch 9 527 CONEEe 13 -gsY4) Ch 523 NHCo4 > Example 14 Knitfabricofa polyesterfiber/cotton (50:50) blend was placed in a dye bath ofthe composition to be given belowandthetemperaturewas raised from 50"C up to 1305C over 40 min. After keeping the dye bath at 1300C for 40 min, it was cooled down to 900C over 10 min, and kept at thattemperaturefor 15 min (dyeing). After the dyeing, the dyed material was washed with water and treated in a liquid containing 2 g/l of "Sunfix 555", a fixing agent manufactured by Sanyo Chemical Industries, Ltd., at 60 C for 20 min.The dyed material thus obtained exhibited very good fastness to washing as will be show in the table below.

Composition ofthe dye bath Compound oftheformula (8) 2% o.w. cotton of Example 1 (o.w. = on weight of) "Kayacelon Red E-GL" 1.6% o.w. polyester (disperse dye manufactured by Nippon Kayaku Co.,) Anhydrous sodium sulfate 20 g/l Bath ratio (adjusted to pH 4.5 with acetic acid and sodium acetate.) Fastness test results Fastness to washing according to JIS L-0844 (1970) A-2 Change in color of the dyed cloth Rating 4-5 Staining of cotton cloth " 4 Stainingofsilkcloth " 4-5 Example 15 Knit cotton fabric was placed in the following dye bath, and was dyed and treated by the same procedure as in Example 14. The dyed material exhibited excellent fastness to washing as is clear from the following table.

Composition ofthe dye bath Compound oftheformula (13) 1% o.w.f.

Of Example 3 (o.w.f. = on weight of fiber) Anhydrous sodium sulfate 10 gel Bath ratio 1:20 Fastness test results Fastness to washing according to JIS L-0844 (1970) A-2 Change in color of the dyed cloth Rating 4-5 Staining of cotton cloth ,, 4 Stainingofsilkcloth " 5 Example 16 Muslin of a polyesterfiber/viscose rayon (65:35) blend was placed inthefollowing dye bath and dyed and treated by the same proce dureas in Example 14.Excellentfastnessto washing was attained as shown in the following table.

Composition ofthe dye bath Compound oftheformula (8) 4% o.w. rayon of Example 1 "Kayacelon Red E-GL" 3% o.w. polyester Anhydrous sodium sulfate 10 g/l Bath ratio 1:15 (adjusted to pH 4.5 with acetic acid and sodium acetate.) Fastness test results Fastness to washing according to JIS L-0844 (1970) A-2 Change in color of the dyed cloth Rating 4-5 Staining of rayon cloth ,, 5 Stainingofsilkcloth " 4-5 Comparative Example Knit cotton fabric was dyed with the com pound of the formula (13) of Example3 and two known dyes, followed by fixing treatment, all in the manner described in Example 14. The washing fastnesses of the dyed fabrics were compared. The following table indicates that the compound ofthe present invention is superior to the known dyes in fastness to washing.

Fastness to washing *1 Test dye Dye Staining of Staining of Cone. *2 cotton cloth silk cloth Compound (13) of Example 3 1% owf 4-3 4 5 Known dyes *3 CI Direct Red 89 1% owf 3-4 1-2 5 " 243 1% owf 3-4 1-2 5 *1 In conformity with JIS L-0844-A-2 *2 Change in color of the dyed cloth *3 Cl Direct Red 89" (Japanese Patent Publication No. 23971/1964, Example 1)

"CI Direct Red 243" (Japanese Patent Publication No. 15712/1977, Example 1)

Claims (13)

1. A disazo compound which, in the free acid form, is represented bythefollowing formula (1):

wherein Xis H orSO3H, Y is a group ofthe formula (2):

(wherein R1 is H, CH3 orC2H5, R2 and Rg are independently H, Cl, CH3, SO3H or COOH) and D isagroupoftheformula (3):

(wherein R4 and R5 are independently H, CH3 or OCH3, Z is CONH, NHCO, SO2CH2 or SO2NH and R6 and R7 are independently H, CH3 or Cl).

2. A disazo compound, according to claim 1, which is represented bythefollowing formula:

wherein Y and Dare as defined above.

3. A disazo compound, according to claim 2, which is represented by the following formula:

wherein R8 and Rg are independently H, CH3, CI or SO3H and R70 and R11 are independently H, CH3orCl.

4. A disazo compound, according to claim 3, which is represented by the following formula:

5. A disazo compound, according to claim 3, which is represented by the following formula:

6. A disazo compound, according to claim 3, which is represented by the following formula:

7. A disazo compound, according to claim 3, which is represented by the following formula:

8. A disazo compound, according to claim 3, which is represented by the following formula:

9. A disazo compound, according to claim 3, which is represented by the following formula:

10. A process for dyeing cellulosic fibers or a cellulosic-fiber component of polyester and cellulosic fiber blend with a disazo compound of theformula (1).

11. A process, according to claim 10, for dyeing cel lulosic-fiber component of polyester and cellulosic fiber blend with a disazo com poundoftheformula (1).

12. A disazo compound as claimed in claim 1 and substantially as described in any one ofthe specific examples herein before set forth.

13. Each and every novel embodiment herein set forth.