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
  • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
  • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
  • C09B62/507—Azo dyes
  • C09B62/513—Disazo or polyazo 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
  • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
  • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
  • C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
  • C09B62/4411—Azo dyes
  • C09B62/4415—Disazo or polyazo 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
  • C09B67/0046—Mixtures of two or more azo dyes
  • C09B67/0047—Mixtures of two or more reactive azo dyes
  • C09B67/005—Mixtures of two or more reactive azo dyes all the reactive groups being not directly attached to a heterocyclic system
• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
  • C09B67/0046—Mixtures of two or more azo dyes
  • C09B67/0055—Mixtures of two or more disazo dyes
  • C09B67/0057—Mixtures of two or more reactive disazo dyes
  • C09B67/0059—Mixtures of two or more reactive disazo dyes all the reactive groups are not directly attached to a heterocyclic system

Definitions

• the present invention relates to compounds of the formula (1 )
• the present invention further relates to intermediates used in the preparation of formula (1 ) a process for the preparation of the compounds of the formula (1 ).
• These dyes can be applied as single dye or as mixture or in combination with other compatible dyestuffs for dyeing a wide variety of fibre materials selected from, cellulose, polyamide or protein fibres and yield dyeings having good allround properties such as excellent washing fatness, low contact staining.
• G1 is hydrogen or hydroxyl
• G2 is hydrogen or hydroxysulfonyl
• G3 is hydrogen or arylazo
• R1 is hydrogen or hydroxysulfonylmethyl
• R2 is hydrogen or hydroxysulfonylmethyl
• D is a radical of a diazo or tetraazo component having in each case at least one anchor radical of the formula S0 2 -Y, wherein Y is vinyl or substituted ethyl, and their use for dyeing or printing hydroxyl-containing or nitrogenous organic substrates, and naphthylamines as intermediates.
• Patent No. 6,537,332 discloses reactive colorants and mixtures of reactive colorants that are suitable for dyeing a wide variety of fibre materials, especially cellulosic fibre materials, and yield dyeings having good all-round properties.
• Ri is a radical of the formula -W-Q wherein
• W is Ci-C 6 Alkylene, which can be substituted by hydroxy
• Q is a carboxylic acid or inorganic acid radical, or a derivative of carboxylic acid or inorganic acid selected , from the series -COOH, -CN, -COOR 3 , -CONH 2 , - CONHR2-, -CONR2R3-, -SO3H, a carbonyl radical of the formula -CO-R 2 , or a radical -O-CO-R3 , -OSO 3 H , -SSO 3 H, -OPO 3 H , which form together with W an organic or inorganic acid ester, wherein R 2 and R 3 are independent from each other C1-C4 Alkyl, which may be further substituted by Sulfo, Sulfato, or Hydroxy, or R 2 and R 3 form together a 5-or 6 ring N- heterocyclic ring such as morpholino, pyrollidino, or piperidino; provided that when Q is Sulfo, W is not methylene;
• Di and D 2 are independently of each other are selected from a radical of the formula (2a), (2b) or (2c), containing a vinylsulfone fibre reactive group,
• R 2 is CrC 4 -Alkyl, CrC 4 -Alkoxy, Carboxy, Halogen, hydroxyl, preferably methoxy or methyl,
• n 2 0, 1 or 2
• n 3 0, 1 or 2
• n 0, 1 or 2
• B is -CO-NR 3 -W 2 - or -NR 3 -CO- W 2 -,
• W 2 is methylene, -(CH 2 ) 2 . 3 , 1 ,3-phenylen, 1 ,4-phenylen,
• R 3 is hydrogen, or methyl
• radicals R 2 may have identical or different meanings, Or a radical of the formula (3a) or (3b), containing a fibre reactive group is of a the heterocyclic type,
• R 4 is hydrogen or methyl
• Z is a pyrimidinyl radical containing leaving groups of the series fluoro, chloro, or methylsulfonyl, and optionally additional substituents such as methyl, chloro, and cyano, or a or triazinyl radical radical of the formula
• X1 is a leaving group from the series chloro, fluoro, or Pyridinyl which may be substituted by Carboxy,
• X2 is chloro, cyanamino, NHQi , NQ 1 Q 2 , -NH-aryi , NR ' -ary 0 -S0 2 Y, -NR " -alk 0 -S0 2 Y, N(alk 0 -S02Y) 2 or
• ary 0 is 1 ,3-phenylen or 1 ,4-phenylen, which may be substituted by methyl, methoxy, carboxy, chloro, or sulfo,
• FT is hydrogen, methyl, or ethyl
• alk o is 1 ,2-ethylen, 1 ,3-propylen or -(CH 2 ) 2 -0-(CH 2 ) 2 -,
• R " is hydrogen, methyl, or phenyl
• aryi is phenyl which may be substituted independent from each other by 1 -2 substituents sulfo, methyl, methoxy, chloro, bromo, carboxy or nitro,
• Qi is CrC 3 -Alkyl, which may be substituted independent from each other by 1 -2 substituents hydroxy, sulfo, sulfato, or acetato,
• Q 2 has one of the meanings of Qi , preferably Q 2 has the same meaning as Qi , or Q 2 forms together with N and Q1 a 5 or 6- membered heterocyclic ring, such as morpholino, piperidiono or pyrrolidino and Y has one of the above defined meanings; Or a radical of the formula
• Figurel provides graphical representation to show Build-Up comparison of example 33 vs Carmine 1 : K/S vs %owf dye concentration
• the dyestuffs of the present invention have the formula (1 )
• Ri is a radical of the formula -W-Q wherein
• W is Ci-C 6 alkylene, which can be substituted by hydroxy
• Q is a radical of a carboxylic acid or inorganic acid, or a derivative of a carboxylic acid or an inorganic acid, from the series -COOH, -CN, -COOR 3 , -CONH 2 , -CONHR 2 -, - CONR2R3-, -SO3H, a carbonyl radical of the formula -CO-R 2 , or a radical -O-CO-R3 , - OSO 3 H , -SSO 3 H, -OPO 3 H, which form together with W an organic or inorganic acid ester, wherein R 2 and R 3 , independently of each other, are C1-C4 alkyl, which may be further substituted by sulfo, sulfato, or hydroxy, or R 2 and R 3 form together a 5-or 6 ring N- heterocyclic ring such as morpholino, pyrollidino, or piperidino.
• W is -CH 2 -, -(CH 2 ) 2 , -CH 2 -CH(CH 3 )-, -CH(CH 3 )- CH 2 -, and
• Q is -COOH, -CN, -CONH 2 , -S0 3 H, and -OS0 3 H .
• preferred radicals W are -(CH 2 ) - and -(CH 2 ) 2 - .
• preferred radicals Q are COOH and S0 3 H.
• D- and D 2 are independently of each other a benzene or naphthyl radical, which are substituted by fibre reactive groups, containing at least one fibre reactive group in both D and D 2 , preferably one fibre reactive group in both D- and D 2 , wherein the fibre reactive groups, independently of each other, are of the vinylsulfone type or heterocyclic type, in particular of the halogenpyrimidinyl or halogentriazinyl reactive group, or of the acrylamide type which is substituted by halogen.
• the fibre reactive group is of the vinylsulfone type, it also includes ⁇ -ethylsulfone substituted in ⁇ -position by a leaving group removable under alkaline medium.
• the fibre reactive group is of heterocyclic type, it is preferably of halogenpyrimidinyl or the halogentriazinyl type.
• Di is a radical of the formula (2a), (2b) or (2c), (2d) or (2e) containing at least one vinylsulfone fibre reactive group,
• R 2 is CrC 4 -alkyl, Ci -C 4 -alkoxy, carboxy, halogen, hydroxyl, preferably methoxy or methyl, n2 is 0, 1 or 2, preferably 0 or 1 ,
• n3 is 0, 1 or 2, preferably 0 or 1 ,
• n 0, 1 or 2
• B is -CO-NR 3 -W 2 - or -NR 3 -CO- W 2 - ,
• the benzene ring carries 0-2 identical or different substituents of Ci-C 3 -alkoxy, preferably methoxy, C C 3 -alkyl, more preferably methyl, carboxy, halogen, or hydroxyl, Ui is hydroxyl or has one of the meanings of Y; preferably Ui is hydroxyl, vinyl or ⁇ - sulfatoethyl.
• R 4 is hydrogen or methyl, preferably hydrogen
• Z is a pyrimidinyl radical containing leaving groups of the series fluoro, chloro, or methylsulfonyl, and optionally additional substituents such as methyl, chloro, and cyano, wherein Z is preferably 2,4-difluoro-pyrimidinyl- , 5-chloro-2,4-difluoro-pyrimidinyl, or 2,4,5-trichloro-pyrimidinyl, or Z is a triazinyl radical of the formula (4)
• Xi is a leaving group from the series chloro or fluoro, or pyridinyl which may be substituted by carboxy
• X 2 is chloro, cyanamino, NHQi , NQ 1 Q 2 , -NH-aryi , NR ' -ary 0 -S0 2 Y, -NR " -alk 0 -S0 2 Y, N (alk 0 -S0 2 Y) 2 or
• ary 0 is 1 ,3-phenylene or 1 ,4-phenylene, which may be substituted by methyl, methoxy, carboxy, chloro, or sulfo,
• FT is hydrogen, methyl, or ethyl
• alk o is 1 ,2-ethylen, 1 ,3-propylen or -(CH 2 ) 2 -0-(CH 2 ) 2 -,
• R " is hydrogen, methyl, or phenyl
• aryi is phenyl which may be substituted independently of each other by 1 -2 substituents sulfo, methyl, methoxy, chloro, bromo, carboxy or nitro, preferably aryi is 3-sulfophenyl, 4- sulfophenyl, 2,4-disulfophenyl or 2,5-disulfophenyl-,
• Qi is CrC 3 -alkyl, which may be substituted independently of each other by 1 -2 substituents hydroxy, sulfo, sulfato, or acetato, preferably Qi is methyl, ethyl, ⁇ - hydroxyethyl, ⁇ -sulfoethyl or ⁇ -sulfatoethyl,
• Q 2 has one of the meanings of Qi , preferably Q 2 has the same meaning as Qi , or
• Q 2 forms together with N and Qi a 5 or 6- membered heterocyclic ring, such as morpholino, piperidiono or pyrrolidino, and Y has one of the above defined meanings,
• Di is a radical of the formula
• D 2 has, independently of the meaning of Di , one of the meanings of Di .
• the dyestuffs wherein the radical WQ is CH 2 S0 3 H, in case and D 2 are radicals of the formula (2a), are already known from prior art and are hence excluded from the scope of the present invention.
• the dyestuffs wherein the radical WQ is CH 2 S0 3 H, in case D- is a radical of the formula (2a) wherein n2 is 2, m is 0, and D 2 a radical of the formula (3a) , wherein Z is a radical of the formula,
• Ci-C 6 alkylene for the radical W there come into consideration, for example, methylene, 1 ,2-ethylene, 1 ,3-propylene, 1 ,2-propylene, 1 ,4-butylene, 1 ,3-butylene, 1 ,2-butylene, 1 ,5- pentylene, 1 ,6-hexylene, 2-hydroxy-1 ,2-ethylene, 3-hydroxy-1 ,3-propylene, 2-hydroxy-1 ,2- propylene, 4-hydroxy-1 ,4-butylene, 3-hydroxy-1 ,3-butylene , 5-hydroxy-1 ,5-pentylene , 6- hydroxy-1 ,6-hexylene , wherein position "1 " is the chemical bond linked with the amino group of formula (1 ).
• Examples for preferred radicals W are methylene, 1 ,2-ethylene, 1 ,3-propylene and 1 ,2- propylene.
• radicals Q are COOH, CN, COOC 2 H 5 , COOCH 3 , CONH 2 ,
• radicals W-Q are -CH 2 -COOH, -CH 2 CH 2 -COOH, -CH(CH 3 )-CH 2 -COOH, CH 2 -CH(CH 3 )-COOH, -(CH 2 ) 3 -COOH, -(CH 2 ) 4 -COOH, -(CH 2 ) 5 -COOH, -(CH 2 ) 6 -COOH, CH 2 CH 2 -S03H, -CH 2 CH 2 -0-S03H, -CH 2 CH 2 -S-S03H, -CH 2 CH 2 -0-P03H, -CH 2 _-CN, - CH 2 CH 2 -CN, -CH(CH 3 )-CH 2 -CN, -CH 2 -CH(CH 3 )-CN,-(CH 2 ) 3 -CN, -(CH 2 ) 4 -CN, -(CH 2 ) 5 -CN,- (CH 2 ) 6 -CN,
• Preferred radicals for W-Q are -CH 2 -COOH, -CH 2 CH 2 -COOH, -CH(CH 3 )-CH 2 -COOH,- CH 2 CH(CH 3 )-COOH, -CH 2 CH 2 -S0 3 H and -CH 2 CH 2 -OS0 3 H.
• radicals (2a) are examples for radicals (2a).
• radicals (2b) are examples for radicals (2b).
• radicals 2d) and (2e) are examples of radicals 2d).
• radicals (3b) are examples for radicals (3b).
• radicals Z in radicals (3a) are examples of radicals Z in radicals (3a).
• FV is -CH 2 -COOH, -CH 2 CH 2 -COOH, -CH(CH 3 )-CH 2 -COOH, -CH 2 -CH(CH 3 )-COOH, - CH 2 CH 2 -CN, -CH 2 CH 2 -CONH 2 , -CH 2 CH 2 -S0 3 H and -CH 2 CH 2 -OS0 3 H, and in particular, especially preferred radicals FV are -CH 2 -COOH , -CH 2 CH 2 -COOH and -CH 2 CH 2 -S0 3 H, the benzene rings(6a and (6b)
• sulfo may additionally carry 1 or 2 substituents of sulfo, methoxy or methyl groups, wherein in particular preferred are benzene rings (6a) which carry as substituents methyl, methoxy , and benzene rings (6b) which carry no substituent or 1 sulfo group,
• V has, independent of the radical V, one of the meanings of the radical V,
• Z- is one of the following radicals
• ⁇ is chloro or fluoro
• X 2 ' is chloro, ⁇ -sulfoethylamino, morpholino or cyanamino
• Qi ' is methyl, ethyl, n-propyl, ⁇ -hydroxyethyl, ⁇ -sulfoethyl or ⁇ -sulfatoethyl,
• Q 2 ' has one of the meanings of Qi , preferably Q 2 has the same meaning as Qi ,
• V and V are vinylsulfonyl or ⁇ -sulfatoethylsulfonyl located in meta or para position to the azo link.
• especially preferred dyestuffs of the formula (5a) are structures of the formula (5a ' ) and (5a " )
• Ri is -(CH 2 ) 2 -COOH or -(CH 2 ) 2 -S0 3 H.
• the present invention includes mixtures of dyestuffs of formula (1 ) with at least one dyestuff of the formula (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g), (1 h), (1 i), (1j) and (1 k), wherein the ratio of the components of these mixtures (1 ):(1 a) is 99:1 to 30:70, preferably
• the ratio of the components of the mixtures (1 ):(1 b) is 99:1 to 85:15, preferably 96:4 to 92:8;
• the ratio of the components of the mixtures (1 ):(1 c) is 99:1 to 85:15, preferably 96:4 to 92:8; the ratio of the components of the mixtures (1 :(1 d) is 99:1 to 90:10, preferably 99:1 to 95:5;
• the ratio of the components of the mixtures (1 :(1 e) is 99:1 to 90:10, preferably 99:1 to 95:5;
• the ratio of the components of the mixtures (1 :(1 f) is 99:1 to 90:10, preferably 99:1 to 95:5;
• the ratio of the components of the mixtures (1 :(1 g) is 99:1 to 85:15, preferably 99:1 to 94:6;
• the ratio of the components of the mixtures (1 :(1 h) is 99:1 to 85:15, preferably 99:1 to 94:6;
• the ratio of the components of the mixtures (1 :(1 i) is 99:1 to 85:15, preferably 99:1 to 94:6;
• the ratio of the components of the mixtures (1 :(1j) is 99:1 to 85:15, preferably 99:1 to 94:6;
• the ratio of the components of the mixtures (1 :(1 k) is 99:1 to 90:10, preferably 99:1 to 95:5, and
• the mixtures may contain several dyestuffs of (1 a) to (1 k), provided that the ratio of (1 ) to the sum of the dyestuffs (1 a) to (1 k) is 99:1 o 25:75, preferably 99:1 to 40:60.
• R 1 ; D-i and D 2 have one of the above defined meanings.
• Especially preferred mixtures of the compounds of formula (1 ) and compounds of formula (1 a) are mixtures of (5a ' ) with (1 a ' ) wherein D1 and D2 have one of the meanings of the radical (2a) and the ratio of the mixing components is 90:10 to 60:40.
• mixtures of the compounds of formula (1 ) and compounds of formula (1 a) are mixtures of (5a “ ) with (1 a " ) wherein D1 and D2 have one of the meanings of the radical (2a) and the ratio of the mixing components is 90:10 to 60:40.
• the dyestuff mixtures may be obtained as reaction mass from synthesis in a one pot azo coupling reaction or by physical mixing of the compounds, preferably as reaction mass from synthesis, and applied without further purification, or purified by isolation, such as salting out from sodium or potassium chloride or sulphate solution, by reverse osmosis treatment or purified at the stage of the intermediate synthesis by crystallization or precipitation from aqueous medium, preferably from acidic solution.
• the dyestuffs of the formula (1 a), (1 e), (1 f), (1 i) and (1j) are already known.
• the dyestuffs of the formula (1 b), (1 c), (1 d), (1 g), (1 h) and (1 k) are new compounds, and are also included as single dyestuff components in the present invention, excluding dyestuffs (1 b) wherein Ri is CH 2 S0 3 H and D1 is a radical of the formula (2a) since it is known from prior art.
• the compounds (1 a) to (1 k) may be formed as byproducts in the manufacturing of the dyestuffs of the present invention, or added to the mixtures after separate manufacturing operation.
• Th resent invention includes intermediates of the formula
• W and Q have one of the above specified meanings.
• W is C 2 -C 6 alkylene, which can be substituted by hydroxy
• the invention also includes mixtures of the compounds of the formula (7) with compounds of the formula (7a) in the ratio 100:0 to 30:70, preferably 99:1 to 55:45.
• the invention also covers the manufacturing process of the new intermediates of formula (7) wherein -W-Q has one of the above described meanings.
• the intermediates of the formula (7) are prepared according to reaction path (8a) by reacting 2-amino-naphthol-7-sulfonic acid with a compound of the formula hal-W-Q, wherein hal is chloro or bromo and W and Q have one of the above meanings, at a temperature of 40-80 °C, and pH of 2-9, preferably 3-5,
• reaction path (8b) by reacting 2-amino-5-naphthol-7-sulfonic acid with a primary amine of the formula H 2 N-W-Q in the presence of a catalyst such as sodium bisulphite, under reaction conditions typical for the Bucherer reaction, at a temperature of 60-130 °C preferably 80-99 °C, and pH of 2-9, preferably 3-6,
• a catalyst such as sodium bisulphite
• reaction path (8c) by reacting 2-amino-5-naphthol-7-sulfonic acid with ⁇ . ⁇ -unsaturated compounds of the formula (9) , wherein R 5 and R 6 are independently of each other hydrogen or methyl, and Q has one of the above meanings, at conditions typical for a Michael addition, a temperature of 60-100 °C, and pH of 2-9, preferably 3-7,
• reaction path (8d) by reacting 2-amino-5-naphthol-7-sulfonic acid with a primary amine of the formula H 2 N-W-OH in presence of a catalyst such as sodium bisulphite, at a temperature of 60-130°C, preferably 80-99°C, and pH of 2-9, preferably 3- 6, followed by esterification, by using typical reagents for synthesis of sulfuric acid or phosphoric acid esters, to yield a compound of the formula (7) wherein Q is sulfato or phosphato. 2. esterification
• reaction path (8c) which yield ⁇ -amino derivatives of carboxylic acid derivatives, such as esters, acids or nitriles are known from Tetrahedron 2004, 60, 383- 387 and from Letters in Organic Chemistry 2007, 4, 54-59, and from the US patent application No. 2 759 913.
• Examples for compounds hal-W-Q are
• 2-sulfoethylamin 2-sulfopropylamin, 3-aminopropionic acid, 2-aminopropionic acid, 4- aminobutyric acid, 3-aminobutyric acid, 2-aminobutyric acid.
• Examples for compounds H 2 N-W-OH are 2-Aminoethanol, 3-aminopropanol, 2- aminopropanol, 4-aminobutanol, 3-aminobutanol.
• inventive products of the formula (1 ) are subsequently prepared by azo coupling of coupling components of the formula (7) according to reaction path (10a) with freshly prepared diazonium salts of the formula D N 2 + and D N 2 + , which are made in the usual way from the aromatic amines D NH ⁇ and D 2 -NH 2 in acidic conditions by use of sodium nitrite and acid, e.g. hydrochloric or sulfuric acid,
• novel dyestuffs can be in the form of the free acid or in the form of their salts. They are preferably in the form of the salts, especially the alkali metal and alkaline earth metal salts, and in particular in the form of their sodium, potassium or lithium salts.
• the novel dyestuffs are preferably used in the form of their alkali metal salts for dyeing and printing fibre materials.
• the present invention provides a process for dyeing from aqueous bath and printing of fibre materials with the dyes of the present invention.
• cellulose natural cellulose fibres such as cotton, linen or hemp, especially cotton, and regenerated cellulose such as viscose or lyocell, polyamide fibres such as nylon 6, nylon 6.6 or protein fibres such as wool or silk are preferred fibre materials.
• the dyes are also suitable for dyeing and printing of fibre blends containing the mentioned cellulose, polyamide or protein fibre materials.
• the dyes of the invention can be applied to and fixed on the fibre material in various ways, in particular in the form of aqueous dye solutions and print pastes. They are suitable for known application techniques which are established for the application of reactive dyes, in particular exhaust method, padding method, whereby the material is impregnated with aqueous, salt containing or salt free solutions of the dyes, and fixed after alkali treatment or in presence of alkali with or without heating, and printing methods, conventional or digital (ink jet) printing.
• the dye and prints are rinsed and thoroughly washed with cold or hot water containing auxiliary agents such as detergents or surfactants that promote the wash-off of unfixed portions.
• the present dyes are of red to rubine colour, and are especially suitable for dyeing in deep shades such as deep red, rubine, dark brown, burgundy, and black shades, applied as single dye or as mixture in the present invention, or in combination with other compatible dyestuffs containing vinylsulfone and/or heterocyclic reactive groups, preferably applied in dichromatic or trichromatic combinations, while exhibiting superior properties in coloration technology compared to known mixtures of state of the art, with regard to achieving very deep shades, and excellent fastness properties.
• alkali used for fixation examples include alkali hydroxide, alkali carbonate, alkali silicate, of which sodium hydroxide, sodium carbonate, sodium silicate are preferred.
• the amount of dye applied in the dye bath can vary according to the desired depth of shade, generally an amount of 0.01 to 10 % per weight of fabric is suitable, and in particular 0.2 to 8% per weight of fabric is preferred.
• the dye bath may contain additions of auxiliaries such as inorganic salt, preferably sodium chloride or sodium sulfate, to support the exhaustion of the dyes onto the fibre material, and in padding process urea, and in printing applications thickening pastes such as alginate thickenings.
• auxiliaries such as inorganic salt, preferably sodium chloride or sodium sulfate, to support the exhaustion of the dyes onto the fibre material, and in padding process urea, and in printing applications thickening pastes such as alginate thickenings.
• the preferred procedure is dyeing from an aqueous batch, in the presence of 20-100 g/L salt, sodium chloride or sodium sulfate, and a liquor ratio of 1 :2 to 1 :50, preferably 1 :3 to 1 :30, at a dye bath pH of 7-13, preferably 9-1 1 , and at a temperature of 40-90 °C, preferably 45-65 °C.
• the dyeing obtained with the dyes of the present invention has excellent fixation yield and excellent build-up.
• the obtained dye-fibre bond is of high stability not only in the acid but also in the alkaline range, also good light fastness and very good wash fastness, even in deep shades, as well as good contact fastness to water and perspiration.
• the dyeing obtained with the dyes of the present invention is dischargeable and can be applied in discharge printing.
• J-acid 2-amino-naphthol-7-sulfonic acid
• chloro acetic acid a solution of 24 parts per weight of 2-amino-naphthol-7-sulfonic acid ("J-acid") in 500 parts per volume of water is charged 10 parts per weight of chloro acetic acid, and the reaction mixture is heated and stirred for 4 h at a temperature of 60-70 °C while the pH value is adjusted to pH 6-7. Hydrochloric acid is added to adjust to pH 1 . The reaction mass is filtered and the compound of the formula
• J-acid 2-amino-naphthol-7-sulfonic acid
• ⁇ -alanine 10 parts per weight of sodium bisulfite
• the reaction mixture is stirred for 30 h at a temperature of 95-98 °C while the pH value is adjusted to pH 7 .
• Caustic soda 33% solution is added to adjust to pH 7, while the product precipitates.
• the reaction mass is filtered and the compound of the formula.
• J-acid 2-amino-naphthol-7-sulfonic acid
• methacrylic acid 9-amino-naphthol-7-sulfonic acid
• J-acid 2-amino-naphthol-7-sulfonic acid
• the dyestuff is isolated in the usual manner by spray drying.
• the dyestuff provides dyeing on cotton in very deep rubine shades and exhibit excellent build-up in very deep shades, and good wash fastness.
• reaction mass is stirred for 4 hrs at pH 1 and 0-5 °C to carry out the 1 st coupling stage. Then the pH value is raised to pH 5-5.5 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-5 °C. The reaction mass is stirred for 1 more hours.
• the dyestuff is isolated in the usual manner by spray drying.
• the dyestuff provides dyeing on cotton in deep red-brown shades and exhibit good build-up in very deep shades, and good wash fastness
• the dyestuff is isolated in the usual manner by spray drying.
• the dyestuff provides dyeing on cotton in deep carmine red shades and exhibit good build-up in very deep shades, and good wash fastness.
• This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10 °C. The diazonium salt is charged to the extent until the second coupling stage is completed.
• the dyestuff is isolated in the usual manner by spray drying.
• the dyestuff provides dyeing on cotton in deep red shades and exhibit good build-up in very deep shades, and good wash fastness.
• This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.5-7.2 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-5 °C. The diazonium salt is charged to the extent until the second coupling stage is completed.
• the dyestuff is isolated in the usual manner by spray drying.
• the dyestuff provides dyeing on cotton in deep rubine shades and exhibit good build-up in very deep shades, and good wash fastness.
• Rubine k max 535) is obtained.
• the dyestuff is isolated in the usual manner by spray drying. The dyestuff provides dyeing on cotton in deep rubine shades and exhibit good build-up in very deep shades, and good wash fastness
• Example 3 is repeated, however, instead of using the intermediate compound A, 33.8 parts per weight of the intermediate compound M is used.
• the dyestuff is isolated in the usual manner by spray drying.
• the dyestuff provides dyeing on cotton in deep red brown shades and exhibit good build-up in very deep shades, and good wash fastness
• This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.5-7.3 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10 ' ⁇ . The diazonium salt is charged to the extent until the second coupling stage is completed.
• cyanuric chloride is dispersed by means of a dispersing aid under vigorous stirring in 500 parts per volume of water, and 300 parts per weight of crushed ice.
• This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.6 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-5 °C. The diazonium salt is charged to the extent until the second coupling stage is completed.
• This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.6 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-5 °C. The diazonium salt is charged to the extent until the second coupling stage is completed.
• 5-Aminomethylen-2-amino-naphthalene-1 -sulfonic acid is condensed with 2,4,6- trifluorotriazine according to EP 526792 at pH 3-4 and 0-5°, and diazotised in the usual manner by means of sodium nitrite and hydrochloric acid at pH 1 and 0-5 °C, and then coupled first coupling stage of example 3 at pH 6.5 and 0-5 °C.
• diazonium salt Approximately half the volume of the diazonium salt is charged until the first coupling stage is completed. Then the remaining diazonium salt dispersion is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10°C. The diazonium salt is charged to the extent until the second coupling stage is completed.
• the dyestuff composition is isolated in the usual manner, by spray drying.
• the dyestuff composition provides on cotton deep red brown shades and exhibit good build-up in deep shades, and good wash fastness.
• the dyestuff composition is isolated in the usual manner, by spray drying.
• the dyestuff composition provides on cotton deep red shades and exhibit excellent build-up in very deep shades, and good wash fastness.
• Scarlet 3 is known from US 6,01 1 ,140, example 34.
• Comparative dyestuffs Orange 1 is known from US6537332, example 27, Scarlet 1 and Scarlet 2 are known from US6537332, example 87/88.
• Fixation yield refers to the degree of fixation on cotton relative to the total amount of dyestuff applied in the dye bath in exhaust dyeing, carried out according to the dyeing examples 1 and 2, in % owf (in parts "of weight fabric") as mentioned in the table.
• the method for assessment of fixation yield is according to the published procedure as described in Dyes and Pigments, 21 (1993), 23 wherein the dyestuff concentration in the dyebath was applied at the same concentration.
• WQ CH 2 COOH
• WQ H CO and PA staining on CO / PA : 4 staining on CO / PA : adjacent fibre material
• 100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a dye bath containing 800 parts of water, 50 parts per weight of sodium chloride, and 3 parts per weight of the dyestuff of example 3. After 30 min at ⁇ ' ⁇ , 15 parts per weight of sodium carbonate is added, and the dyeing temperature is maintained at 60 °C for another 45 min.
• the dyed fabric is then rinsed in a fresh bath of 2000 parts warm water, neutralized by adding 1 part per weight of acetic acid, and soaped in another fresh bath of 2000 parts of water in presence of a conventional detergent for 5 min. at 95 °C, and dried.
• 100 parts per weight of cotton fabric is padded with a padding liquor, applying a liquor pickup of 70% per weight of fabric, in a freshly prepared padding liquor containing 1000 parts of water, 50 parts per weight of the dyestuff of example 1 , 30 parts per weight of sodium carbonate and 10 parts per weight of sodium hydroxide 50% solution.
• the padded fabric is then rolled, covered to keep it wet, and stored for a period of 16 to 24 h. Finally the fabric is rinsed and soaped in the same manner as outlined in dyeing example 1 . A deep red dye with excellent fastness to washing and very low contact staining is obtained.

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