TRIPHENODIOXAZINE COMPOUNDS AND DYEING OR PRINTING OF FIBER MATERIALS USING THE SAME

Abstract: A dioxazine compound represented by the following formula in a free acid form, wherein R is halogen, alkyl, alkoxy or sulfo, and W is wherein V is a direct linkage or in which R₃ is hydrogen or alkyl, X is a direct linkage or an aliphatic, alicyclic, araliphatic or aromatic bridging group, Y is unsubstituted or substituted phenylene or naphthylene, Z is -SO₂CH=CH₂, -SO₂CH₂CH₂OSO₃H or the like, Q is sulfo, hydroxy, halogen, alkoxy, phenoxy or amino, and each R₁ and R₂ independently are hydrogen or alkyl, which is useful for dyeing or printing fiber materials with advantages to give dyed or printed materials superior in fastness properties such as chlorine fastness.

Description: The present invention relates to triphenodioxazine compounds, a process for producing the same and a process for dyeing or printing fiber materials using the same. More specifically, the present invention relates to triphenodioxazine compounds having two so-called vinylsulfone type fiber reactive groups linked to the chromophor via triazinyl groups; said compounds being useful for dyeing or printing fiber materials such as cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leathers and mixed fibers thereof to give dyed or printed products superior in light fastness, wet fastness and chlorine fastness. Triphenodioxazine reactive dyes useful for dyeing or printing hydroxyl or amide group-containing fiber materials are known as disclosed in, for example, United States Patent No. 3,223,470, British Patent No. 1,368,158 and Published Examined Japanese Patent Application No. 60-18359 which corresponds to Published Unexamined Japanese Patent Application No. 57-14654 and is abstracted in C.A. 97 (1982) 78169. However, these known reactive dyes of this kind insufficiently meet with required dyeing performances such as level-dyeing property and build-up property, as well as dyeing rate and fastness properties, particularly the chlorine fastness. The present inventors have undertaken extensive studies to find triphenodioxazine compounds sufficiently meeting such needs, particularly compounds capable of giving dyed or printed products of hydroxyl group-containing fiber materials which are superior in fastness properties, particularly chlorine fastness, and which also show superior dye performance. As a result they have found specific triphenodioxazine compounds meeting such needs. The present invention provides a triphenodioxazine compound represented by the following formula (I) in the free acid form, where R is halogen, alkyl, alkoxy or sulfo, and W is a group of the general formula wherein the various symbols have the following meaning : X is a straight or branched aliphatic, alicyclic, araliphatic or aromatic bridging group (unsubstituted or substituted), m is 0 or 1, Y is an unsubstituted or substituted phenylene or naphthylene, Z is -SO₂CH=CH₂ or -SO₂CH₂CH₂Z₁ in which Z₁ is a group which may be split off by the action or an alkali, Q. is sulfo, hydroxy, halogen, alkoxy, or unsubstituted or substituted phenoxy or amino, and R₁ R₂ and R₃ independently of one another are each hydrogen or alkyl. A further object of the present invention is a process for producing the triphenodioxyazine compound of the formula (I), which comprises subjecting any one of an intermediate dioxazine compound represented by the following formula (II) in the free acid form, wherein R, R₁, R₃, X and m are as defined above, and an amine compound represented by the following formula (III), wherein R₂, Y and Z are as defined above, and a compound, if any, represented by the following formula (IV), H - Q₁ (IV) wherein Q₁ is sulfo, hydroxy, alkoxy, or unsubstituted or substituted phenoxy or amino, to first condensation with a 2,4,6-trihalogeno-s-triazine, followed by second and third condensation, if any, with the remaining starting compound(s). The present invention also provides a process for dyeing or printing hydroxyl or amide group-containing materials, which comprises using the triphenodioxazine compound of the formula (I). In the above formula (I), the alkyl and alkoxy represented by R are those having 1 to 4 carbon atoms. With respect to the symbol R, preferred groups are chloro, methyl, methoxy, ethoxy and sulfo. The alkyl represented by R₁, R₂ and R₃ is the one having 1 to 4 carbon atoms unsubstituted or substituted with hydroxy, cyano, C 1-4 alkoxy, halogen, carbamoyl, carboxy, C 1-4 alkoxycarbonyl, C 1-4 alkylcarbonyloxy, sulfo or sulfamoyl. Preferred examples of R₁, R₂ and R₃ are those as disclosed in Published Unexamined Japanese Patent Application No. 59-122549. Of these, preferred are hydrogen, methyl and ethyl. With respect to the symbol X, the aliphatic bridging group can contain a hetero atom, and can be additionally substituted by sulfo, carboxy, methyl, methoxy or optionally substituted phenyl. Examples thereof are as follows. The araliphatic bridging group can contain a hetero atom, and can be additionally substituted by sulfo, carboxy, methyl, methoxy or optionally substituted phenyl. Examples thereof are as follows. The aromatic bridging group can be additionally substituted by sulfo, carboxy, methyl, methoxy or optionally substituted phenyl. Examples thereof are as follows. Of these bridging groups represented by the symbol X, preferred are C 2-6 alkylene groups, particularly groups as ethylene and propylene, and phenylene unsubstituted or substituted by sulfo. With respect to the symbol Q, the halogen includes chloro and fluoro, and the alkoxy group has preferably 1 to 4 carbon atoms. The phenoxy is unsubstituted or substituted(once or twice)by chloro, bromo, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy. The amino group includes, for example, unsubstituted amino, alkylamino, cycloalkylamino, aralkylamino, arylamino and N,N-disubstituted amino such as N,N-dialkylamino, N-alkyl-N-cycloalkylamino and N-alkyl-N-arylamino, as well as heterocyclic ring-containing amino which heterocyclic ring may be further addition-condensed with a homocyclic ring, and N-heterocyclic ring-constituting amino which may contain additional hetero atoms (in the present invention, the term "N-heterocyclic ring-constituting amino" is intended to mean such that the nitrogen atom of the amino is a member forming a heterocyclic ring). In the above definition with respect to the amino, the alkyl is a straight or branched one preferably having 1 to 4 carbon atoms, and preferred examples of the cycloalkyl, aralkyl and aryl are cyclohexyl, benzyl, phenethyl, phenyl and naphthyl, respectively. Examples of the heterocyclic ring are furan, thiophene, pyrazole, pyridine, pirimidine, quinoline, benzimidazole, benzthiazole and benzoxazole. The N-heterocyclic ring-constituting amino is preferably a six-membered ring which may contain an additional hetero atom such as nitrogen, oxygen and sulphur. The above-mentioned alkyl, cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclic ring may be unsubstituted or substituted with halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁-C₄ alkyl, C₁-C₄ alkoxy, acylamino(such as acetyl-, propionyl-, crotyl- or benzoyl-amino),ureido, hydroxy, carboxy, sulfomethyl and/or sulfo. Preferred examples of the amino represented by Q are -NH₂, methylamino, ethylamino, propylamino, butylamino, hexylamino, β-methoxyethylamino, β-ethoxyethylamino, γ-methoxypropylamino, N,N-dimethylamino, N,N-diethylamino, β-chloroethylamino, β-cyanoethylamino, N,N-di-β-hydroxyethylamino, β-hydroxyethylamino, γ-hydroxypropylamino, benzylamino, phenethylamino, cyclohexylamino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-propyl-N-phenylamino, N-butyl-N-phenylamino, N-β-cyanoethyl-N-phenylamino, N-ethyl-2-methylphenylamino, N-ethyl-4-methylphenylamino, N-ethyl-3-sulfophenylamino, N-ethyl-4-sulfophenylamino, phenylamino, toluidino, xylidino, chloroanilino, anisidino, phenetidino, 2-, 3- and 4-sulfoanilino, 2,5-disulfoanilino, sulfomethylanilino, N-sulfomethylanilino, 3- and 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxyl-4-sulfophenylamino, 2-methoxy-5-sulfophenylamino, 2-methyl-5-sulfophenylamino, 4-sulfonaphthyl-(1)-amino, 3,6-disulfonaphthyl-(1)-amino, 3,6,8-trisulfonaphthyl-(1)-amino, 4,6,8-trisulfonaphthyl-(1)-amino, 6-sulfonaphthyl-(2)-amino, 4,8-disulfonaphthyl-(2)-amino, 3,6,8-trisulfonaphthyl-(2)-amino, 4,6,8-trisulfonaphthyl-(2)-amino, pyridyl-(2)-amino, morpholino, piperidino, piperazino, ethanolamino, methanolamino, N,N-diethanolamino, N,N-dimethanolamino, N-ethanol-N-methylamino and N-ethyl-N-methanolamino. Of the groups represented by the symbol Q, particularly preferred are halogen groups such as chloro. The phenylene groups represented by Y can be unsubstituted or substituted (once or twice) with methyl, ethyl, methoxy, ethoxy, chloro, bromo or sulfo, and the naphthylene groups may be unsubstituted or substituted (once) with sulfo. Examples thereof are as follows: In the above formulae, the asterisked bonds indicate a linkage to the group. Of these, preferred are phenylene, unsubstituted or substituted by methyl, methoxy or sulfo. The group which may be split off by the action of an alkali, which is represented by Z₁, includes sulfato, thiosulfato, phosphato, acetoxy and halogen. In the present invention, a particularly preferred group Z is β-sulfatoethylsulfonyl, which may be partially replaced by vinylsulfonyl. Among the triphenodioxazine compounds represented by the formula (I), particularly preferred are compounds represented by the following formula (I-1) in their free acid form, wherein R₄ is chloro, methyl, methoxy, ethoxy or sulfo, X₁ is ethylene, propylene or sulfophenylene, R₅ is hydrogen, methyl or ethyl, R₆ is hydrogen, methyl, methoxy or sulfo, and m is 0 or 1. The triphenodioxazine compound of the formula (I) may be in the form of a free acid or a salt, particularly an alkali metal or alkaline earth metal salt such as a sodium, potassium and lithium salt. The triphenodioxazine compound of the formula (I) can be preferably produced in the following manner: The intermediate dioxazine compound of the formula (II) and the amine compound of the formula (III) together with or without the compound of formula (IV) can be subjected to condensation reactions in order with a 1,3,5-trihalogeno-s-triazine to obtain the desired dioxazine compound of the formula (I). Although the condensation reactions can be carried out under optional reaction conditions and the order of the condensation reactions is not limited, the first condensation can be preferably carried out at a temperature of -10° to 40°C and at a pH ranging from 2 to 9, and the second condensation at temperature of 0° to 70°C and at a pH ranging from 2 to 9. If the compound of the formula (IV) is used, the third condensation can be preferably carried out at a temperature of 10° to 100°C and at a pH ranging from 2 to 7. The order of the condensation reactions can be determined preferably in such a manner that any compound having the lowest reactivity to the 1,3,5-trihalogeno-s-triazine is subjected to the first condensation reaction. The intermediate dioxazine compound of the formula (II) can be readily prepared in a conventional manner, for example, in the following manner: An aniline compound represented by the following formula (V) in the free acid form, wherein R, R₁, R₃ X and m are as defined above, is subjected to condensation with chloranil, thereby obtaining a dianilide compound represented by the following formula (VI) in the free acid form, wherein R, R₁, R₃ X and m are as defined above. The dianilide compound isolated, preferably followed by drying, is then subjected to ring-closure, if desired, in the presence of an oxidizing agent, thereby obtaining the desired intermediate dioxazine compound (II). After completion of the reaction, the desired triphenodioxazine compound-containing reaction mixture may be formed into a liquid commercial product, if desired, after removing inorganic salts and by addition of a stabilizer or a dyeing improver. The liquid product obtained or the aforesaid reaction mixture may be subjected to evaporation such as spray-drying, thereby obtaining a commercial product in the form of a powder. Alternatively according to a conventional manner, the reaction mixture may be formed into either a liquid or solid powder form commercial product by salting-out using an electrolyte. The triphenodioxazine compound (I) of the present invention is fiber-reactive and useful for dyeing or printing hydroxyl group-containing and amide group-containing materials, preferably in a fibrous form or a mixed fibrous form. The hydroxyl group-containing materials include natural or synthetic hydroxyl group-containing materials such as cellulose fiber materials, regenerated products thereof and polyvinyl alcohol. Examples of the cellulose fiber materials are cotton and other vegetable fiber such as linen, hemp, jute and ramie fibers. Examples of the regenerated cellulose fibers are viscose staple and filament viscose. The amide group-containing materials include synthetic or natural polyamide and polyurethane. Examples of the materials, particularly in the fibrous forms, are wool and other animal furs, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4. The dyeing may be carried out in a suitable manner, which can be selected from conventional manners depending on the physical and chemical properties of said fiber materials. For example, cellulose fiber materials can be dyed using the triphenodioxazine compound by an exhaustion dyeing, padding including cold batch-up dyeing or printing method. The exhaustion dyeing can be carried out at a relatively low temperature in the presence of an acid binding agent such as sodium carbonate, trisodium phosphate, sodium hydroxide and the like, if desired, using a neutral salt such as sodium sulfate, sodium chloride and the like, together with a hydrotropic agent, a penetrant or a level dyeing agent. The neutral salt usable for promoting the exhaustion may be added to a dye bath before or after temperature reaching a desired level for the dyeing, if desired, dividedly. The padding can be carried out by padding the fiber materials at ambient temperature of an elevated temperature, and after drying, steaming or dry-heating the materials to perform the dye-fixation. The printing can be carried out in a one-phase or two-phase manner. The one-phase printing may be conducted by printing the fiber materials with a printing paste containing an acid binding agent such as sodium hydrogencarbonate and the like, followed by steaming at a temperature of 100° to 160°C. The two-phase printing may be conducted by printing the fiber materials with a neutral or weakly acidic printing paste, and passing the materials through a hot alkaline bath containing an electrolyte or over-padding the materials with an alkaline padding liquor containing an electrolyte, followed by a steaming or dry-heating treatment. For the preparation of the printing paste, a paste or emulsifier such as sodium alginate, starch ether and the like may be used, if desired, together with a conventional auxiliary agent such as urea and/or a dispersing agent. The acid binding agent useful for fixing the compound of the present invention on the cellulose fiber materials includes water-soluble basic salts consisting of alkali or alkaline earth metals and inorganic or hydroxides and alkali metal salts of inorganic or organic acids having a weak or medium strength. Particularly preferred are sodium salts and potassium salts. Examples thereof are sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, sodium formate, potassium carbonate, sodium dihydrogenphosphate, disodium hydrogenphosphate, trisodium phosphate, sodium silicate, sodium trichloroacetate and the like. The dyeing of natural or synthetic polyamide and polyurethane fiber materials can be carried out by performing exhaustion in an acid or weak acid bath, while controlling the pH value, and then making the bath neutral, or in some cases alkaline to perform the fixation. The dyeing temperature ranges usually from 60° to 120°C. In order to achieve a level dyeing, there may be used a conventional level dyeing agent such as condensation product between cyanuric chloride and 3 times by mole of aminobenzene-sulfonic acid or aminonaphthalenesulfonic acid, or an addition product between stearylamine and ethylene oxide, and the like. The present triphenodioxazine compounds can be characterized by excellent dye performance in the dyeing and printing of fiber materials, particularly cellulose fiber materials. For example, the triphenodioxazine compounds can give dyed or printed products superior in fastness properties such as light fastness, perspiration-light fastness, wet fastness including washing resistance, peroxide-washing resistance, perspiration resistance, acid-hydrolysis resistance and alkali resistance, chlorine fastness, abrasion fastness and iron-fastness, with superior build-up, level-dyeing and washing-off properties. Moreover, the present triphenodioxazine compound is superior in solubility and exhaustion and fixation abilities, and robust so that a shade to be obtained can hardly be affected by changes in dyebath conditions such as dyeing temperatures, pH, amounts of inorganic salts and bath ratios, and therefore dyed or printed products with a constant quality can be obtained with superior reproducibility. The present invention is illustrated in more detail with reference to the following Examples, which are only illustrative, but not limiting. In the Examples, all parts and % values are by weight. Example 1 A solution of 1,4-diamino-2-methoxybenzene-5-sulfonic acid (109 parts) in water (700 parts) was added dropwise to a dispersion of chloranil (64.6 parts) in ethanol (4000 parts), and the mixture was heated up to 60°C and kept at this temperature to complete the reaction. Thereafter, the reaction mixture was cooled to deposit crystals. The crystals isolated were mixed with 28% oleum (800 parts), and the mixture was heated upto 45°C and kept at this temperature to complete the reaction. The reaction mixture was then poured into ice water, followed by salting-out to deposit crystals, which were separated to obtain an intermediate dioxazine compound of the following formula in the free acid form. The intermediate dioxazine compound (60.5 parts) and cyanuric chloride (19 parts) were allowed to react with each other in water (500 parts), while hydrochloric acid generated was neutralized using sodium carbonate. Into the reaction mixture was added 1-aminobenzene-3-β-sulfatoethylsulfone (28 parts), and the components of the mixture were allowed to react with each other. Thereafter, by salting-out and isolation of the crystals one obtained a triphenodioxazine compound of the following formula in the free acid form. Example 2 The triphenodioxazine compound obtained in Example 1 (each 0.1, 0.3 and 0.6 parts respectively) was dissolved in water (200 parts), and sodium sulfate (10 parts) and cotton (10 parts) were added thereto. The bath was heated to 60°C, and then sodium carbonate (4 parts) was added thereto. Respective dyeings were continued at that temperature for 1 hour. Thereafter, the cotton taken out was washed with water and soaped, followed by washing with water, to obtain in each case a dyed product of a reddish blue color superior in fastness properties, particularly in chlorine fastness, light fastness and perspiration-light fastness with a superior build-up property. Examples 3 to 26 Example 1 was repeated, except that 1,4-diamino-2-methoxybenzene-5-sulfonic acid used in Example 1 was replaced by the aniline compound of the formula (V) as shown in the following table. One obtained the intermediate dioxazine compound (II),also as shown below, which was subjected to condensation with the amine compound (III) also as shown in the following table instead of 1-aminobenzene-3-β-sulfatoethylsulfone, whereby the corresponding triphenodioxazine compound was obtained. Example 27 The triphenodioxazine compound obtained in Example 12 (0.3 parts) was dissolved in water (200 parts), and cotton (10 parts) was added thereto. The bath was heated to 50°C, and 30 minutes thereafter, sodium carbonate (4 parts) was added thereto. Dyeing was continued at that temperature for 1 hour. Thereafter, the cotton taken out was washed with water and soaped to obtain a dyed product of a reddish blue color superior in fastness properties, particularly such as chlorine fastness, light fastness and perspiration-light fastness, with a superior build-up property. Example 28 The triphenodioxazine compounds obtained in each of Examples 3 to 11 and 13 to 26 (0.1, 0.3 and 0.6 parts respectively) were dissolved in water (200 parts), and sodium sulfate (10 parts) and cotton (10 parts) were added thereto. The bath was heated to 60°C, and then sodium carbonate (4 parts) was added thereto. Respective dyeings were continued at that temperature for 1 hour. The cotton taken out was washed with water and soaped, followed by washing with water and drying to obtain dyed products each of a blue color superior in fastness properties, particularly such as chlorine fastness, light fastness and perspiration-light fastness, with a superior build-up property. Example 29 The intermediate dioxazine compound (120 parts) obtained in the same manner as in Example 1 and metanilic acid (12.7 parts) were added to water (500 parts) in this order, and the mixture was heated up to 70° to 80°C, while hydrochloric acid generated was neutralized with sodium carbonate. The components were allowed to react with each other at that temperature. Thereafter, salting-out of the reaction mixture gave a triphenodioxazine compound of the following formula in the free acid form. Example 30 The triphenodioxazine compound obtained in Example 29 (0.3 parts) was dissolved in water (200 parts), and cotton (10 parts) was added thereto. The bath was heated to 50°C. 30 Minutes thereafter, sodium carbonate (4 parts) was added thereto, and dyeing was continued at that temperature for 1 hour. Thereafter, the cotton taken out was washed with water and soaped to obtain a dyed product of a reddish blue color, superior in fastness properties, particularly chlorine fastness, light fastness and perspiration-light fastness, with a superior build-up property. Example Nos. 31 to 48 Example 29 was repeated using the intermediate dioxazine compound of the formula (II) as shown in the following table, which had been obtained in manner similar to that of Example 1, except for using the aniline compound (V), also as shown below, instead of 1,4-diamino-2-methoxybenzene-5-sulfonic acid, and by replacing the metanilic acid with the compound (IV), also as shown below, whereby the corresponding triphenodioxazine compound was obtained. Example 49 The triphenodioxazine compound obtained in Example 37 (0.3 parts)was dissolved in water (200 parts), and cotton (10 parts) was added thereto. The bath was heated to 50°C. 30 Minutes thereafter, sodium carbonate (4 parts) was added thereto, and dyeing was continued at that temperature for 1 hour. Thereafter, the cotton taken out was washed with water and soaped to obtain a dyed product of a reddish blue color superior in fastness properties, particularly in chlorine fastness, light fastness and perspiration-light fastness, with a superior build-up property. Example 50 Each of the triphenodioxazine compounds obtained in Examples 31 to 36 and 38 to 48 (0.1, 0.3 and 0.6 parts respectively)were dissolved in water (200 parts), and sodium sulfate (10 parts) and cotton (10 parts) were added thereto. The bath was heated to 60°C, and then sodium carbonate (4 parts) was added thereto. Respective dyeings were continued at that temperature for 1 hour. Thereafter, the cotton taken out was washed with water and soaped, followed by washing with water and drying, to obtain dyed products each of a blue color superior in fastness properties, particularly in chlorine fastness, light fastness and perspiration-light fastness, with a superior build-up property. Example 51 To water (200 parts) were added 2-hydroxy-4,6-dichloro-s-triazine (17.1 parts) and the same intermediate compound as in Example 1 (60.5 parts.) The components were allowed to react with each other. Then, 1-aminobenzene-3-β-sulfatoethylsulfone (28 parts) was added thereto to perform the reaction. Thereafter, salting-out gave a triphenodioxazine compound of the following formula in the free acid form. Example 52 Repeating the procedure of Example 51, using 2-methoxy-4,6-dichloro-s-triazine (18.5 parts), the same intermediate dioxazine compound (60.5 parts) and 1-aminobenzene-3-β-sulfatoethylsulfone (28 parts), there was obtained a triphenodioxazine compound of the following formula in the free acid form. Example 53 A condensate between the intermediate dioxazine compound (60.5 parts) and cyanuric chloride (19 parts) was prepared and mixed with sodium sulfite to replace one chloro group of the condensate by a sulfo group. Then 1-aminobenzene-3-β-sulfatoethylsulfone (28 parts) was added to replace another chloro group of the condensate. Salting-out of the resulting reaction mixture gave a triphenodioxazine compound of the following formula in the free acid form. Examples 54 to 65 Using the intermediate dioxazine compound (II) and the amine compound (III)as shown in the following table, and by following Examples 51 to 53 respectively resulted in the corresponding triphenodioxazine compound. Example 66 The triphenodioxazine compound obtained in Example 53 (0.3 parts)was dissolved in water (200 parts), and cotton (10 parts) was added thereto. The bath was heated to 50°C, and 30 minutes thereafter, sodium carbonate (4 parts) was added thereto. Dyeing was continued at that temperature for 1 hour. The cotton taken out was washed with water and soaped to obtain a dyed product of a reddish blue color superior in fastness properties, particularly in chlorine fastness, light fastness and perspiration-light fastness with a superior build-up property. Example 67 Each of the triphenodioxazine compounds obtained in Examples 51 and 52 to 65 (0.1, 0.3 and 0.6 parts respectively) were dissolved in water (200 parts), and sodium sulfate (10 parts) and cotton (10 parts) were added thereto. The bath was heated to 60°C, and then sodium carbonate (4 parts) was added thereto. Respective dyeings were continued at that temperature for 1 hour. The cotton taken out was washed with water and soaped, followed by washing with water and drying to obtain dyed products each of a blue color excellent in fastness properties, particularly in chlorine fastness, light fastness and perspiration-light fastness, with a superior build-up property. Example 68 Composition of color paste Triphenodioxazine compound obtained in Example 1 5 parts Urea 5 parts Sodium alginate (5%), thickener 50 parts Hot water 25 parts Sodium hydrogencarbonate 2 parts Water (balance) 13 parts Mercerized cotton broad cloth was printed with the color paste having the above composition, pre-dried, steamed at 100°C for 5 minutes, washed with hot water, soaped, again washed with water and dried, thereby obtaining a printed product of a blue color excellent in fastness properties.

Claims: Claims for the following Contracting States : BE, CH, DE, FR, GB, IT, LI, NL, SE A dioxazine compound represented by the following formula (I) in the free acid form, wherein R is halogeno, alkyl, alkoxy or sulfo, and W is wherein X is a straight or branched aliphatic, alicyclic, araliphatic or aromatic bridging group unsubstituted or substituted, m is 0 or 1, Y is unsubstituted or substituted phenylene or naphthylene, Z is -SO₂CH=CH₂ or -SO₂CH₂CH₂Z₁ in which Z₁ is a group which can be split off by the action of an alkali, Q is sulfo, hydroxy, halogen, alkoxy, or unsubstituted or substituted phenoxy or amino, and each R₁, R₂ and R₃ independently are hydrogen or alkyl. A dioxazine compound according to Claim 1, wherein R is chloro, methyl, methoxy, ethoxy or sulfo. A dioxazine compound according to Claim 1, wherein X is ethylene, propylene or phenylene unsubstituted or substituted once or twice by sulfo. A dioxazine compound according to Claim 1, wherein each R₁, R₂ and R₃ independently are hydrogen or methyl or ethyl. A dioxazine compound according to Claim 1, wherein Y is phenylene unsubstituted or substituted once or twice by methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, sulfo or carboxy, or naphthylene unsubstituted or substituted by sulfo. A dioxazine compound according to Claim 1, wherein Z is -SO₂CH=CH₂ or -SO₂CH₂CH₂OSO₃H. A dioxazine compound according to Claim 1, wherein Q is chloro. A dioxazine compound according to Claim 1, wherein R is chloro, methyl, methoxy, ethoxy or sulfo, and W is wherein X₁ is ethylene, propylene or sulfophenylene, R₅ is hydrogen, methyl or ethyl, R₆ is hydrogen, methyl, methoxy or sulfo, and m is 0 or 1. A process or producing a dioxazine compound represented by the formula (I) in the free acid form according to claim 1, which comprises subjecting any one of the intermediate dioxazine compound represented by the following formula (II) in the free acid form, wherein R, R₁, R₃, X and m are as defined in Claim 1 and an amine compound represented by the following formula (III), wherein R₂, Y and Z are as defined in Claim 1 and optionally a compound, represented by the following formula (IV), H - Q₁ (IV) wherein Q₁ is sulfo, hydroxy, alkoxy, unsubstituted or substituted phenoxy or amino, to a first condensation with a 2,4,6-trihalogeno-s-triazine, optionally followed by second and third condensation with the remaining starting compound(s). A process for dyeing or printing hydroxyl or amide group-containing materials, which comprises using a dioxazine compound represented by the formula (I) in the free acid form according to claim 1. Hydroxy or amide group-containing materials dyed or printed by the process of Claim 10. Claims for the following Contracting State : ES A process for producing a dioxazine compound represented by the following formula (I) in the free acid form wherein R is halogeno, alkyl, alkoxy or sulfo, and W is wherein X is a straight or branched aliphatic, alicyclic, araliphatic or aromatic bridging group unsubstituted or substituted, m is 0 or 1, Y is unsubstituted or substituted phenylene or naphthylene, Z is -SO₂CH=CH₂ or -SO₂CH₂CH₂Z₁ in which Z₁ is a group which can be split off by the action of an alkali, Q is sulfo, hydroxy, halogen, alkoxy, or unsubstituted or substituted phenoxy or amino, and each R₁, R₂ and R₃ independently are hydrogen or alkyl, which comprises subjecting any one of the intermediate dioxazine compound represented by the following formula (II) in the free acid form, wherein R, R₁, R₃, X and m are as defined above, and an amine compound represented by the following formula (III), wherein R₂, Y and Z are as defined above, and optionally a compound, represented by the following formula (IV), H - Q₁ (IV) wherein Q₁ is sulfo, hydroxy, alkoxy, unsubstituted or substituted phenoxy or amino, to a first condensation with a 2,4,6-trihalogeno-s-triazine, optionally followed by second and third condensation with the remaining starting compound(s). A process for producing a dioxazine compound represented by the formula (I) in the free acid form, according to Claim 1, wherein R is chloro, methyl, methoxy, ethoxy or sulfo. A process for producing a dioxazine compound represented by the formula (I) in the free acid form, according to Claim 1, wherein X is ethylene, propylene or phenylene unsubstituted or substituted once or twice by sulfo. A process for producing a dioxazine compound represented by the formula (I) in the free acid form, according to Claim 1, wherein each R₁, R₂ and R₃ independently are hydrogen methyl or ethyl. A process for producing a dioxazine compound represented by the formula (I) in the free acid form, according to Claim 1, wherein Y is phenylene unsubstituted or substituted once or twice by methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, sulfo or carboxy, or naphthylene unsubstituted or substituted by sulfo. A process for producing a dioxazine compound represented by the formula (I) in the free acid form, according to Claim 1, wherein Z is -SO₂CH=CH₂ or -SO₂CH₂CH₂OSO₃H. A process for producing a dioxazine compound represented by the formula (I) in the free acid form, according to Claim 1, wherein Q is chloro. A process for producing a dioxazine compound represented by the formula (I) in the free acid form, according to Claim 1, wherein R is chloro, methyl, methoxy, ethoxy or sulfo, and W is wherein X₁ is ethylene, propylene or sulfophenylene, R₅ is hydrogen, methyl or ethyl, R₆ is hydrogen, methyl, methoxy or sulfo, and m is 0 or 1. A process for dyeing or printing hydroxyl or amide group-containing materials, which comprises using a dioxazine compound represented by the formula (I) in a free acid form according to claim 1. Hydroxy or amide group-containing materials dyed or printed by the process of Claim 9.

Inventors: HARADA, NAOKI, OMURA, TAKASHI, SAWAMOTO, HIROKAZU
Applicants: SUMITOMO CHEMICAL COMPANY, LIMITED
Application year: 1988
Main classification: C09B62
IPC codes: D06P1, C09B62, C09B19