Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
  • C09B62/06—Anthracene dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/918—Cellulose textile

Definitions

• This invention relates to a series of reactive triazine dyestuffs capable of being absorbed and chemically fixed on cellulose fibers by either a cold or warm dyeing process.
• the dyestulfs of the present invention are prepared by a quaternization reaction of the reactive triazine dyestuffs having the general formula:
• X is selected from the group consisting of H, CH OCH and OC H n is an integer from 1 to 4, and chromogen means the colored residue of a dyestulf selected from the group consisting of azo-dyestulfs, metallized-azo-dyestutfs, anthraquinone dyestuffs and phthalocyanine dyestuffs.
• the reactive quaternized dyestuffs of the present invention have the general formula:
• Chromogen-NH-C wherein X and n have the above mentioned meanings and m is 1 or 2.
• the chromogen may be an azoic, azoicmetallized anthraquinone or phthalocyanine dyestuff.
• the reactive quaternized dyestuffs are prepared by reacting a metal salt of isonicotinic acid with the reactive dyestulfs of the general Formula I.
• the class of reactive dyestuffs of the present invention can be advantageously applied both at warm and cold temperatures.
• isonicotinic acid as the quaternizing agent of the above mentioned chlorotriazine dyestuffs generally produces the following advantages with respect to the use of other quaternizable tertiary amines, namely:
• isonicotinic acid is odorless, and therefore the dye baths both cold and warm, are completely free of disagreeable or irritating odors.
• isonicotinic acid also from the point of view of the costs, is advantageous because the excess of isonicotinic acid used in the quaternization reaction may be easily recovered from the mother liquors by filtration, after acidification of these mother liquors, and then it may be reused.
• the quaternization is generally carried out by dissolving the reactive dyestuff to be used in a 2% solution of a metal salt of the isonicotinic acid.
• the reaction temperature may be varied within wide wide limits, but it is preferably kept between 60 and C.
• the reaction rate is obviously influenced by the selected temperature and may be controlled by chromatographic analysis.
• EXAMPLE 1 2 parts of isonicotinic acid are dissolved in parts of water at 70 C. together with 0.64 part of 100% NaOH.
• the solution is kept at this temperature for a whole night (about 15 hours); the dyestutf after salting with NaCl is separated by filtration and dried at 60 C. It may be also separated by direct drying.
• the dyestuff obtained dyes cotton at a temperature of 3540 C. with very good tinctorial yields, in a red shade having very good fastness to washing.
• the dyestuff to be quaternized used in the process of this example can be obtained as follows:
• the temperature of the reaction between d 6 b i bl pouring d o i f id mass is p between 0 and C": and the P between acceptor solutions (20% Na CO solution; 1 N NaOH 5 and 6 y Suitable Pouring dTOPWiSe 0f the acid acceptor solution; NaHCO solution and if desired, Na acetate).
• the dyestutf to be quarternized, used in the process a neutral sol tion of 0.1 mol (20,9 parts) of of the present example, can be obtained as follows:
• the agitation is continued until the dissolution is complete about 2 hours), always keeping the temperature of the reaction mass between 0 and 2 C. and the pH between 5 and 6.
• the solution is cooled to 2-3 C. and 6.9 parts (0.1 mol) of sodium nitrite (in the form of an aqueous 20% w./v. solution), 80 parts ice and 25.7 parts of 21 B. HCl are added in a thin stream.
• reaction mass is agitated for about 10 minutes at the temperature of 3-4 C.
• the suspension of the diazo thus obtained is added within about 30 minutes to a solution of 0.1 mol of carbamylisogarnma acid (in the form of its sodium salt) in 350 parts by volume, together with 150 parts NaCl.
• the solution within 2-3 hours, is added with a 10% solution of Na CO introduced dropwise and keeping the pH at the value of 7-7.5.
• the dyestufl is separated by filtration and after washing with a 7% brine is dried in a stove at 40 C. for 48 hours.
• the dyestuif to be quaternized used in the process of this example can be obtained as follows:
• the solution of the monoazo thus obtained (volume 500 parts by volume) is heated at 60 C. and is mixed with a 1 equivalent solution of CuSO -5H O (25 parts and with a solution containing 2 equivalents of crystallized sodium acetate (27 parts).
• the metallization is complete within 1-2 hours at 60-65 C. and a pH of about 6.
• the separation of the Cu complex is carried out after cooling and 10% (w./v.) salting, by filtration.
• the cake of the meta'llized monoazo dissolves in 500 parts by volume water, at a pH of 7-7.5.
• the solution of 0.13 mol of the monocondensation product between cyanuric chloride and the sodium salt of anilinomethanesulfonic acid, prepared according to the modalities described in Example 1 is added at room temperature.
• the solution thus obtained is mixed with 14 parts (0.1 mol) of crystallized sodium acetate, is heated on a water bath at 40-45 C. and is maintained at this temperature for 2-4 hours in order to complete the reaction.
• the pH is kept at 5.8-6 by addition of alka-lies (N82C03, Nell-[CO etc.; volume about parts).
• the quaternized dyestutf thus obtained dyes cotton from an aqueous bath at 35-40 C.. with very good tinctorial yields in a yellow shade having very good fastness to wet treatments.
• the dyestuff to be quaternized used in the process of this example can be obtained as follows:
• cyanuric chloride 0.1 mol (18.44 parts) of cyanuric chloride is dissolved in 100-150 parts by volume acetone and the solution is poured on water and ice (200-600 parts in total).
• the neutral solution consisting of 0.1 mol (20.9 parts) of C H NHCH SO Na in 100-130 parts by volume water, cooled at 2-4 C. with ice is poured dropwise. During the addition the temperature of the reaction mass is maintained between 0 and 2 C. and the pH between 5 and 6 by suitable pouring dropwise of acid acceptor solutions. (20% solution of Na CO 1 N NaOH, NaHCO and if desired Na acetate).
• the agitation is continued until the dissolution is complete (about 2 hours), keeping the temperature of the reaction mass between 0 and 2 C. and the pH between 5 and 6.
• the solution thus obtained is neutralized with 1 -N NaOH or with 10% solution of Na CO and is purified, if necessary, from the traces of insoluble residue.
• the monocondensation product the sodium salt of the 4,6-dichloro-s-triazin-2-yl-anilinomethanesulfonic acid is obtained.
• the whole is heated at about 40 C. and by keeping this temperature constant, the pH is always adjusted between 5.5 and 6.0 by gradual addition of 50-55 parts by volume of a 10% w./v. solution of sodium carbonate.
• reaction mass is agitated for about 10 minutes at the temperature of 3-4 C.
• dichloro-4-sulfophenyl)-3-methyl-5-pyrazolone in 150 parts Water and 13 parts sodium carbonate, previously cooled at about 5 C. and added immediately before the coupling with 60 parts of crystallized sodium acetate.
• the dyestufr is then precipitated by salting out, filtered under vacuum and dried as much as possible and then dried in a stove at 35-40" C. for 48 hours.
• a dye bath is prepared by dissolving 2 parts by Weight of the dyestulf prepared according to the Example 5, in 2000 parts by volume of water at the temperature of 35 C.
• 100 parts of the cellulose material are introduced in the dye bath; after minutes 60 parts of anhydrous Na SO are added; after minutes 60 parts of anhydrous Na SO are added; after minutes 15 parts of Na CO are added; after 60 minutes 15 parts of Na CO are added.
• the bath is maintained at 35 C. for a further hour, in order to complete the fixing of the dyestuff, and then the material is soaped for 30 minutes at boiling with a 3% soap solution.
• the material is rinsed thoroughly with water.
• a cellulose material dyed in a yellow shade having very good fastness to Wet treatment is obtained, with very good tinctorial yields.
• EXAMPLE 7 A dye bath is prepared by dissolving 2 parts by weight of the dyestuif prepared according to the Example 5, in 2000 parts by volume of water, at the temperature of C.
• 100 parts of the cellulose material are introduced in the dye bath; after 15 minutes at the temperature of 50 C., parts of anhydrous Na SO is added; after 30 minutes at the temperature of 60 C., 60 parts of anhydrous Na SO are added; after 45 minutes at the temperature of C., 15 parts of Na CO are added; after 60 minutes at the temperature of C., 15 parts of Na CO are added.
• the bath is kept at 80 C. for one further hour.
• the material is soaped for 30 minutes at the boiling with a soap solution. The material is well rinsed with water.
• a cellulose material dyed in a yellow shade having very good fastness to wet treatment is obtained, with very good tinctorial yields.
• EXAMPLE 8 2 parts of isonicotinic acid and 0.64 part of NaOH are dissolved in 100 parts of water, at 80 C. 5 parts of the dyestuff:
• the mass is then slowly added, at 05 C., to a solution (kept at 05 C.) of the compound obtained according to the description of Example 1 by condensation between 0.1 mol of cyanuric chloride and 0.1 mol of the sodium salt of anilinomethanesulfonic acid added with 10 parts of sodium bicarbonate.
• the temperature is then permitted to rise to 20-25 C., and is kept at this value until the condensation is ended.
• the dyestuff obtained dyes cotton at the temperature of 60 C., with good tinctorial yields, in a turquoise shade having very good fastness to washing.
• the dyestuff to be quaternized used in this process can be obtained as follows:
• Pc means copper phthalocyanine
• the solution thus obtained is slowly added at 05 C. to a solution (which is also kept at 05 C.) of the condensation product between 0.1 mol of cyanuric chloride and 0.1 mol of the sodium salt of the anilinomethanesulfonic acid added with 10 parts of sodium bicarbonate.
• the condensation product between cyanuric chloride and the sodium salt of the anilinomethanesulfonic acid can be prepared, for instance, by dissolving, in 500 parts of water, 0.1 mol of the sodium salt of the anilinomethanesulfonic acid and adding 17 parts of sodium bicarbonate and successively, at a temperature of 05 C., a suspension (kept at 05 C.) of 0.1 mol of cyanuric chloride in 1500 parts of water.)
• the whole is agitated for some hours at increasing temperature up to 2025 0, till a sample shows that the reaction is ended.
• the reaction product is separated by salting.
• a dye bath is prepared by dissolving 2 parts by weight of the dyestuff prepared according to the Example 10, in 2000 parts by volume of water at the temperature of 60 C.
• 100 parts of the cellulose material are introduced in the dye bath; after 15 minutes 60 parts of anhydrous Na SO are added; after 30 minutes 60 parts of anhydrous Na SO are added; after 45 minutes 15 parts of Na CO are added; after 60 minutes 15 parts of Na CO are added.
• the bath is maintained at 60 C. for one further hour, in order to complete the fixing of the dyestuff and then the material is soaped for 30 minutes at the boiling point with a 3% soap solution.
• a cellulose material dyed in a turquoise shade having very good fastness to wet treatment is obtained with very good tinctorial yields.
• Example 8 With the same procedure, the quaternized dyestuff of Example 8 can also be applied.
• a process for dyeing cellulose textile materials comprising applying thereto a dyestufl? having the formula O SOsNa wherein X is selected from the group consisting of H, CH OCH and OC H n is an integer from 1 to 4; m is 1 or 2 and the chromogen is selected from the group consisting of azo dyestuffs, metallized-azo-dyestuffs, anthraquinone dyestufis, and phthalocyanine dyestuffs.
• a dyeing process according to claim 2, wherein the acid-binding agent is selected from the group consisting of an alkaline hydroxide, an alkaline carbonate, an alkaline bicarbonate, and an alkaline triphosphate.
• a dyeing process according to claim 4, wherein the acid-binding agent is selected from the group consisting of an alkaline hydroxide, an alkaline carbonate, an alkaline bicarbonate, and an alkaline triphosphate.
• Cellulose textile materials in particular fibers, dyed or printed with one or more of the reactive dyestuffs having the formula wherein X is selected from the group consisting of H, CH OCH and OC H n is an integer from 1 to 4; m is 1 or 2 and the chromogen is selected from the group consisting of azo dyestuffs, metallized-azo-dyestuffs, anthraquinone dyestuffs, and phthalocyanine dyestuffs.

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• Organic Chemistry (AREA)
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• Plural Heterocyclic Compounds (AREA)

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• 1965
  • 1965-07-05 NL NL6508612A patent/NL6508612A/xx unknown
  • 1965-07-06 GB GB28611/65A patent/GB1049084A/en not_active Expired
  • 1965-07-14 DE DE19651544352 patent/DE1544352A1/de active Pending
  • 1965-07-16 SE SE9409/65A patent/SE314148B/xx unknown
  • 1965-07-16 BE BE667043D patent/BE667043A/xx unknown
  • 1965-07-16 CH CH1005965A patent/CH422198A/it unknown
  • 1965-07-16 US US472668A patent/US3416875A/en not_active Expired - Lifetime
• 1968
  • 1968-06-05 US US749899*A patent/US3522232A/en not_active Expired - Lifetime
• 1970
  • 1970-03-19 US US21222A patent/US3639398A/en not_active Expired - Lifetime

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