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
  • C09B62/4401—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
  • 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
  • C09B62/4413—Non-metallized monoazo 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
  • C09B67/0055—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
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
  • D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
  • D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/58—Material containing hydroxyl groups
  • D06P3/60—Natural or regenerated cellulose
  • D06P3/66—Natural or regenerated cellulose using reactive dyes

Definitions

• the present invention relates to novel isomeric mixtures of reactive dyes of yellow colour, to mixtures containing said dyes, to ink compositions comprising said dyes and dye mixtures, to processes for the preparation thereof and to the use thereof in dyeing or printing textile fibre materials.
• the novel isomeric mixtures of reactive dyes according to the invention are suitable for the dyeing or printing of nitrogen-containing or hydroxy-group-containing fibre materials and yield on such materials dyeings or prints having a good build-up behaviour, a high fixation rate, excellent washing off properties of the unfixed dyes and good fastness properties.
• Reactive dyes which can be used for the dyeing and printing of hydroxyl-group- containing or nitrogen-containing fibre materials are known and described, for example, in EP 0 567 036. However, these dyes, when used alone, do not provide high degrees of fixing.
• the present invention is therefore based on the problem of providing new mixtures of reactive dyes that are suitable especially for the reproducible dyeing and printing of fibre materials in the desired colour shades and fulfil the above indicated requirements to the highest possible extent.
• the dye mixtures should also yield dyeing having good build-up properties, high fixation rates, good washing off properties of the unfixed dyes, and good all-round fastness properties, for example fastness to chlorine and to peroxide.
• the reactive dyes according to the invention also show satisfactory stability to various dyeing parameters.
• the invention relates to an isomeric mixture of at least one dye of the formula
• - Xi and X2 are independently a halogen atom
• A1 are independently a hydrogen atom or a C1-C4 alkyl
• R1 , R2 are independently -H, -SO3M, a C1-C4 alkyl, a C1-C4 alkoxy, -COOH, a halogen atom,
• M is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.
• Z1, Z2 are -SO2- CH2-CH2-OSO3M.
• Z1 , Z2 are located in para-position to the azo group and R1, R2 are located in ortho-position to the azo group.
• the isomeric mixture responds to formula wherein
• Xi and X2 are independently -Cl or -F,
• the isomeric mixture responds to formula (101 -a) or formula (101-b) or a salt thereof, or a mixture thereof:
• the invention further relates to a mixture of isomeric dye mixtures comprising:
• - X3 is a halogen atom
• - A3 is a hydrogen atom or a C1-C4 alkyl
• R3, R4 are, independently -H, -SO3M’, a C1-C4 alkyl, a C1-C4 alkoxy,
• CH CH 2 , -NH-(CH 2 ) 2 -O-(CH 2 ) 3 NHCO-(CH 2 )3-SO 2 -(CH 2 ) 2 -Y’ wherein Y’ is a group removable under alkaline conditions; - M’ is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.
• At least one dye mixture of formula (II) is a dye mixture of formula (201-a) or formula (201 -b) or a salt thereof, or a mixture thereof:
• the invention also relates to a dye mixture comprising at least:
• the dye mixture comprises at least:
• (B) 40 to 80 % by weight, preferably 45 to 75 % by weight, in particular 50 to 70 % by weight, of at least one reactive dye different from the dye mixture of formula (I) and from the dye mixture of formula (II), each percentage being based on the sum total of all dyes.
• the invention further relates to an aqueous inks comprising at least an isomeric mixture of at least one dye of the formula (I) as defined above and in details hereunder, or a mixture of dyes as defined above and in details here-under.
• the invention also relates to the use of at least one reactive dye of formula (I) as defined above and in details here-under, or a mixture of dyes as defined above and in details here-under, or an ink as defined above and in details here-under, in the dyeing or printing of textile material such as hydroxyl-group-containing or nitrogencontaining fibre material, especially cellulosic fibre material.
• the invention further relates to a textile dyed or printed with at least one reactive dye of formula (I) as defined above and in details here-under, or a mixture of dyes according as defined above and in details here-under, or an ink as defined above and in details here-under.
• the invention also relates to a process for dyeing or printing of hydroxy-g roupcontaining or nitrogen-containing fibre materials, which process comprises using at least one reactive dye of formula (I) as defined above and in details here-under, or a mixture of dyes as defined above and in details here-under, or an ink as defined above and in details here-under.
• Another object of the invention is a process for the preparation of a mixture of isomeric dyes of at least one dye of the formula (I) as defined above and in details here-under, which comprises: (a) diazotising a compound of the formula (1) wherein R represents R1, R2 or R3, Z represents Z1, Z2 or Z3; and reacting the diazonium salt so obtained with a coupling component of formula (2) whereby an azo compound of formula (3) is obtained
• step (b) condensing the azo compound of formula (3) prepared in step (a) with a compound of formula
• step (c) condensing the compound of the formula (5) prepared in step (b) with the compound of formula (6)
• Another object of the invention is a process for the preparation of a mixture of isomeric dye mixtures of at least one dye of the formula (I) and of at least one dye of the formula (II) as defined above and in details here-under, which comprises:
• step (b) condensing the azo compound of formula (3) prepared in step (a) with a compound of formula (4)
• step (c) condensing the compound of the formula (5) prepared in step (b) with the mixture of compounds of formula (6) and (7)
• the present invention accordingly relates to a new isomeric mixture of at least one dye of the formula (I): Wherein
• - Xi and X2 are independently a halogen atom
• A1 are independently a hydrogen atom or a C1-C4 alkyl
• R1 , R2 are independently -H, -SO3M, a C1-C4 alkyl, a C1-C4 alkoxy, -COOH, a halogen atom,
• M is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.
• the isomeric mixture of at least one reactive dye of formula (I) according to the invention provides very good build-up properties, high fixation rates, good washing off properties of the unfixed dyes, and good all-round fastness properties.
• the COOH moiety substituted to the central phenyl cycle of the dye according to the formula (I) advantageously greatly increases the solubility of the dye in polar solvents, whilst the colouring properties of the dye remain the same, in comparison to the same dye without substitution with a COOH moiety.
• the same comparison shows that the dye of formula (I), where the COOH moiety is substituted to the central phenyl cycle, shows a greater affinity to fibre, allowing for a more effective dye.
• the isomeric mixture of reactive dyes of formula (I) comprises reactive dyes with the same chemical formula and thus the same carbon number, but with (substituted)phenyldiazo- moiety and/or Z1, Z2, R1 , R2 groups attached at different positions on the phenyl ring.
• isomeric mixture means a composition comprising more than one isomer of a reactive dye.
• the "isomeric mixture of at least one reactive dye” optionally contains isomers of more than one reactive dye of formula (I).
• the isomeric mixture contains more than one (i.e., two or more) isomers of a reactive dye of formula (I) and also can contain more than one (i.e., two or more) isomers of a different reactive dye of formula (I).
• Different reactive dyes of formula (I) have different chemical formulae comprised in formula (I) and thus may have a different carbon number.
• an isomeric mixture of at least one reactive dye of formula (I) includes a p- vinylsulfonyl reactive dye of formula (I) and its isomers and a p-sulfatoethylsulfonyl reactive dye of formula (I) and its isomers (the isomers having the sulfonic substituent and/or diazo substituents attached at different positions on the phenyl ring).
• the dyes of formula (I), of which is composed the isomeric mixture contain at least 2, preferably from 2 to 4 and especially 4, sulfo groups, which are each present either in free acid form or, preferably, in salt form.
• Suitable salts, represented by M are, for example, alkali metal, alkaline earth metal or ammonium salts, salts of an organic amine, or mixtures thereof. Examples that may be mentioned are sodium, lithium, potassium or ammonium salts, a mono-, di- or tri-ethanolamine salt or mixed Na/Li or Na/Li/NF salts.
• C1-C4 alkyl is meant a saturated, linear or branched hydrocarbon- containing chain comprising from 1 to 4 carbon atoms.
• the hydrocarbon- containing chain is linear.
• the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl or t-butyl. More preferably, the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, n-butyl.
• the C1-C4 alkyl group is methyl or ethyl.
• C1-C4 alkoxy is meant a saturated, linear or branched hydrocarbon- containing chain comprising from 1 to 4 carbon atoms and substituted by an oxygen atom.
• the hydrocarbon-containing chain is linear.
• the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, i- propoxy, n-butoxy, s-butoxy, i-butoxy or t-butoxy. More preferably, the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, n-butoxy.
• the C1-C4 alkoxy group is methoxy or ethoxy.
• the term “halogen” refers to a fluorine atom, a chlorine atom or a bromine atom, preferably a fluorine atom or a chlorine atom.
• halogen represented by the independent variables Xi, X2 and also as a possible choice for the independent variables R1 , R2, there come into consideration, for example, fluorine or chlorine, preferably chlorine.
• a group Y removable under alkaline conditions may be selected from the group consisting of -Cl, -Br, -F, -OSO3M, -SSO3M, -OCO-CH3, -OPO3M2, -OCO-CeHs, - OSC>2-(Ci-C4alkyl) or -OSC>2-N(Ci-C4alkyl)2.
• Y is selected from the group consisting of -Cl, -OSO3M, -SSO3M, -OCO-CH3, -OCO-CeHs or -OPO3M2, more preferably -Cl or -OSO3M, wherein M has the meanings given above.
• Z1, R1 and (Z2, R2) are independently (- SO2-Y; -SO3M), wherein Y and M are as defined above and here-under.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein the fibre-reactive groups Z1, Z2 are located in para-position to the azo group.
• Z1 , Z2 are preferably -SO2-CH2-CH2-OSO3M.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein R1 , R2 are located in ortho-position to the azo group.
• R1 , R2 are preferably -SO3M.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein the diazo groups are located in ortho - position and/or in para-position on the phenyl cycles, with regards to the central chain.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein R1 and/or R2 are located in ortho - position on the terminal phenyl cycles, with regards to the diazo groups.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (I), wherein Z1 and/or Z2 are located in para - position on the terminal phenyl cycles, with regards to the diazo groups.
• a preferred embodiment of the present invention relates to an isomeric mixture of reactive dyes of formula (I), wherein Ai, A2 are H.
• A1, A2 are H,
• R1 , R2 are -SO3M
• X is a fluorine atom
• M is hydrogen, an organic salt, an alkali metal or one equivalent of an alkaline earth metal.
• variables of formula (I) also apply to variables of formula (IA).
• a favorite isomeric mixture of dyes of formula (I) is an isomeric mixture of dyes of formula (101 -a) or (101-b) or salts thereof:
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (101 -a) or (101-b), wherein the diazo groups are located in ortho-position and in para-position on the phenyl cycles, with regards to the central chain.
• the end product can optionally also be subjected to a transformation reaction.
• a transformation reaction is, for example, the conversion of a vinylatable reactive group -SO2-Y, -SO2-Y1 and -SO2-Y2 into its vinyl form by treatment with dilute sodium hydroxide solution, such as, for example, the conversion of the p- chloroethylsulfonyl radical or -sulfatoethylsulfonyl radical into the vinylsulfonyl radical.
• dilute sodium hydroxide solution such as, for example, the conversion of the p- chloroethylsulfonyl radical or -sulfatoethylsulfonyl radical into the vinylsulfonyl radical.
• Such reactions are known per se.
• Those transformation reactions are generally affected in a neutral to alkaline medium at a temperature of, for example, from 20 to 70°C, at a pH of, for example, from 6 to 14.
• a favorite isomeric mixture of reactive dyes of formula (101 -a) is an isomeric mixture of dyes of formula (101-a1) and (101-a2) or a salt thereof:
• a favorite isomeric mixture of reactive dyes of formula (101-b) is an isomeric mixture of dyes of formula (101-b1) and (101-b2) or a salt thereof, wherein (101-b1) corresponds to the mono- or di-vinyl form of (101-a1) and wherein (101-b2) corresponds to the mono- or di-vinyl form of (101-a2).
• the isomeric mixtures of dyes according to the invention dye the support to which they are applied in a golden-yellow shade having a high degree of fixation and good all-round fastness properties, in particular washing-fastness, chlorine and oxygen fastness.
• the isomeric mixture of dyes of formula (I) exhibits a high compatibility with other reactive dyes and can therefore be applied in combination with other dyes in order to adjust a specific shade or in dichromatic or trichromatic mixtures to provide a variety of chromatic tones.
• the invention further relates to a dye mixture comprising:
• - X3 is a halogen atom
• - A3 is a hydrogen atom or a C1-C4 alkyl
• R3, R4 are, independently -H, -SO3M’, a C1-C4 alkyl, a C1-C4 alkoxy,
• CH CH 2 , -NH-(CH 2 ) 2 -O-(CH 2 ) 3 NHCO-(CH 2 )3-SO 2 -(CH 2 ) 2 -Y’ wherein Y’ is a group removable under alkaline conditions;
• - M’ is hydrogen or a salt, or a mixture of salts, of an organic or inorganic cation.
• the isomeric mixture of reactive dyes of formula (II) comprises reactive dyes with the same chemical formula and thus the same carbon number, but with (substituted)phenyldiazo- moiety and/or Z3, R3, R4, COOH groups attached at different positions on the phenyl ring.
• isomeric mixture means a composition comprising more than one isomer of a reactive dye.
• the "isomeric mixture of at least one reactive dye” optionally contains isomers of more than one reactive dye of formula (II).
• the isomeric mixture contains more than one (i.e., two or more) isomers of a reactive dye of formula (II) and also can contain more than one (i.e., two or more) isomers of a different reactive dye of formula (II).
• Different reactive dyes of formula (II) have different chemical formulae comprised in formula (II) and thus may have a different carbon number.
• an isomeric mixture of at least one reactive dye of formula (II) includes a - vinylsulfonyl reactive dye of formula (II) and its isomers and a p-sulfatoethylsulfonyl reactive dye of formula (II) and its isomers (the isomers having the sulfonic substituent and/or diazo substituents attached at different positions on the phenyl ring).
• the dyes of formula (II) contain at least 2, preferably from 2 to 3 and especially 3, sulfo groups, which are each present either in free acid form or, preferably, in salt form.
• Suitable salts are, for example, alkali metal, alkaline earth metal or ammonium salts, salts of an organic amine, or mixtures thereof. Examples that may be mentioned are sodium, lithium, potassium or ammonium salts, a mono-, di- or tri-ethanolamine salt or mixed Na/Li or Na/Li/NH4 salts.
• C1-C4 alkyl is meant a saturated, linear or branched hydrocarbon- containing chain comprising from 1 to 4 carbon atoms.
• the hydrocarbon- containing chain is linear.
• the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl or t-butyl. More preferably, the C1-C4 alkyl group is selected from the group formed by methyl, ethyl, n-propyl, n-butyl.
• the C1-C4 alkyl group is methyl or ethyl.
• C1-C4 alkoxy is meant a saturated, linear or branched hydrocarbon- containing chain comprising from 1 to 4 carbon atoms and substituted by an oxygen atom.
• the hydrocarbon-containing chain is linear.
• the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, i- propoxy, n-butoxy, s-butoxy, i-butoxy or t-butoxy. More preferably, the C1-C4 alkoxy group is selected from the group formed by methoxy, ethoxy, n-propoxy, n-butoxy.
• the C1-C4 alkoxy group is methoxy or ethoxy.
• halogen represented by the variable X3 and also as a possible choice for the variable R3, there come into consideration, for example, fluorine or chlorine, preferably chlorine.
• a group Y’ removable under alkaline conditions may be selected from the group consisting of -Cl, -Br, -F, -OSO3M’, -SSO3M’, -OCO-CH3, -OPO3M’2, -OCO-CeHs, - OSC>2-(Ci-C4alkyl) or -OSC>2-N(Ci-C4alkyl)2.
• Y’ is selected from the group consisting of -Cl, -OSO3M’, -SSO3M’, -OCO-CH3, -OCO-CeHs or -OPO3M’2, more preferably -Cl or -OSO3M’, wherein M’ has the meanings given above.
• Z3, R3 is (-SO2-Y’ ; -SO3M’), wherein Y’ and M’ are as defined above and here-under.
• the fibre-reactive group Z3 is located in para-position to the azo group.
• Z3 is preferably -SO2-CH2-CH2-OSO3M’.
• a preferred embodiment of the present invention is directed to a mixture wherein, in the reactive dye of formula (II), R3 is located in ortho-position to the azo group.
• R3 is preferably -SO3M’.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein the diazo group is located in orthoposition and/or in para-position on the phenyl cycles, with regards to the central chain.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein R3 is located in ortho - position on the terminal phenyl cycles, with regards to the diazo groups.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein Z3 is located in ortho - position on the terminal phenyl cycles, with regards to the diazo groups.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein the COOH group is located in orthoposition on the phenyl cycles, with regards to the central chain.
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (II), wherein R4 is located in meta-position on the phenyl cycles, with regards to the central chain.
• a preferred embodiment of the present invention relates to a mixture of reactive dyes, wherein in the dye of formula (II), A3 is H.
• dyes of formula (II) particularly preferred are dyes of formula (HA)
• X3 is -Cl or -F
• variables X3, Y3, Y’, M’ of formula (II) also apply to variables of formula (HA).
• a favorite isomeric mixture of dyes of formula (II) is an isomeric mixture of dyes of formula (201 -a) or (201 -b) or a salt thereof:
• a preferred embodiment of the present invention is directed to an isomeric mixture of reactive dyes of formula (201 -a) or (201 -b), wherein the diazo group is located in ortho-position and in para-position on the phenyl cycles, with regards to the central chain.
• the end product can optionally also be subjected to a transformation reaction.
• a transformation reaction is, for example, the conversion of a vinylatable reactive group -SO2-Y3 into its vinyl form by treatment with dilute sodium hydroxide solution, such as, for example, the conversion of the p-chloroethylsulfonyl radical or p -sulfatoethylsulfonyl radical into the vinylsulfonyl radical.
• Those transformation reactions are generally affected in a neutral to alkaline medium at a temperature of, for example, from 20 to 70°C, at a pH of, for example, from 6 to 14.
• a favorite isomeric mixture of reactive dyes of formula (201 -a) is an isomeric mixture of dyes of formula (201-a1) and (201-a2) or a salt thereof:
• a favorite isomeric mixture of reactive dyes of formula (201 -b) is an isomeric mixture of dyes of formula (201 -b1) and (201 -b2) or a salt thereof, wherein (201 -b1) corresponds to the vinyl form of (201-a1) and wherein (201-b2) corresponds to the vinyl form of (201 -a2).
• the invention relates to a mixture of isomeric dye mixtures comprising isomeric dye mixtures of formula (I) and isomeric dye mixtures of formula (II) wherein the compounds of formula (I) and the compounds of formula (II) are present in ratio (I) : (II) from 9:1 to 1:9, preferably 3:1 to 1 :9, more preferably 1 :1 to 1 :8, further preferably 1:1 to 1:6, wherein the ratios are expressed as molar equivalent value.
• the invention relates to a mixture of isomeric dye mixtures comprising isomeric dye mixtures of formula (IA) and isomeric dye mixtures of formula (IIA) wherein the compounds of formula (IA) and the compounds of formula (IIA) are present in ratio (IA) : (IIA) from 9:1 to 1:9, preferably 3:1 to 1:9, more preferably 1 :1 to 1 :8, further preferably 1:1 to 1 :6, wherein the ratios are expressed as molar equivalent value.
• the invention further relates to a dye mixture comprising:
• (A2) a mixture of isomeric dye mixtures of at least one dye of the formula (I) and of at least one dye of the formula (II), and further comprising:
• (B) at least one reactive dye different from the dye mixture of formula (I) and from the dye mixture of formula (II).
• the invention further relates to a dye mixture comprising:
• (B) 40 to 80 % by weight, preferably 45 to 75 % by weight, in particular 50 to 70 % by weight, of at least one reactive dye different from the dye mixture of formula (I) and from the dye mixture of formula (II), each percentage being based on the sum total of all dyes.
• Brown C.l. R BR 7, C.l. R BR 11 , C.l. R BR 19, C.l. R BR 37, C.l. R BR 46, C.l. R BR 48, C.l. R BR 49, C.l. R BR 51;
• the dye mixture according to the invention comprises one or more dyes selected from C.l. R BL 220, C.l. R BL 235, C.l. R.BI 285, C.l. R BL 19 ,C.I. R BL 279, C.l. R RE 286, C.l. R RE 287, C.l. R RE 289 and R YE 222 as component (B).
• the present invention further relates to a process for the preparation of the mixture of reactive dye of formula (I), which comprises:
• A1 and/or A2 are different from H, then a derivative of the molecule (6) bearing appropriate substituents on NH2 groups should be used.
• the invention also relates to a method for preparing a mixture of isomeric dye mixtures of at least one dye of the formula (I) and of at least one dye of the formula (II), wherein said method comprises the same steps a) and b) as recited above and further comprises one step (c) consisting in condensing the compound of the formula (5) prepared in step (b) with the mixture of compounds of formula (6) and formula (7)
• variables A, R, Z and X in the method for preparing isomeric dye mixtures (I) and (I) correspond to favourite choices of, respectively, A1 , A2, A3, R1 , R2, R3, Z1 , Z2, Z3 and X1, X2, X3 as above defined in the description of these compounds.
• the fibre-reactive dyes according to the invention, and dye mixtures comprising them are suitable for dyeing and printing, in particular for printing, a wide variety of materials, especially hydroxyl-group-containing or nitrogen-containing fibre materials.
• materials especially hydroxyl-group-containing or nitrogen-containing fibre materials.
• Examples include paper, silk, leather, wool, polyamide fibres and polyurethanes, and especially all types of cellulosic fibre materials.
• Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, and cellulose and regenerated cellulose.
• the dyes according to the invention are also suitable for dyeing or printing hydroxyl-group-containing fibres present in blend fabrics, for example blends of cotton and polyester fibres or polyamide fibres.
• the present invention also concerns an aqueous ink comprising the dyes of formula (I) according to the invention, or dye mixtures comprising them, and to the use of such inks in an ink-jet printing method for printing a variety of substrates, especially textile fibre materials, the definitions and preferences indicated above applying to the dyes and dyes mixtures, the inks and the substrates.
• the dyes of formula (I) according to the invention show very good build-up behaviour, a high end build-up and a high degree of fixation, especially in printing applications on cellulosic fibre materials, as well as an improved stability towards varying printing parameters.
• the dyes of formula (I) according to the invention, and dye mixtures comprising them are also suitable as colorants for use in recording systems.
• Such recording systems are, for example, commercially available ink-jet printers for paper or textile printing, or writing instruments, such as fountain pens or ballpoint pens, and especially ink-jet printers.
• the dyes according to the invention are first brought into a form suitable for use in recording systems.
• a suitable form is, for example, an aqueous ink, which comprises the dyes of formula (I) according to the invention, or the dye mixtures comprising them, as colorants.
• the inks can be prepared in customary manner by mixing together the individual components in the desired amount of water.
• substrates there come into consideration the above-mentioned hydroxyl- group-containing or nitrogen-containing fibre materials, especially cellulosic fibre materials.
• the fibre materials are preferably textile fibre materials.
• plastics-coated paper e.g. Epson Ink-jet Paper, Epson Photo Paper, Epson Glossy Paper, Epson Glossy Film, HP Special Ink-jet Paper, Encad Photo Gloss Paper and Ilford Photo Paper.
• Plastics films are, for example, transparent or cloudy/opaque. Suitable plastics films are, for example, 3M Transparency Film.
• the viscosity or other physical properties of the ink especially properties that have an influence on the affinity for the substrate in question, to be adapted accordingly.
• the dyes of formula (I) according to the invention, or the dye mixtures comprising them, used in the aqueous inks should preferably have a low salt content, that is to say they should have a total content of salts of less than 0.5 % by weight, based on the weight of the dyes.
• Dyes that have relatively high salt contents as a result of their preparation and/or as a result of the subsequent addition of diluents can be desalted, for example by membrane separation procedures, such as ultrafiltration, reverse osmosis or dialysis.
• the inks preferably have a total content of dye or dye mixture according to the invention from 1 to 35 % by weight, especially from 1 to 30 % by weight and preferably from 1 to 20 % by weight, based on the total weight of the ink.
• the preferred lower limit in this case is a limit of 1.5 % by weight, preferably 2 % by weight and especially 3 % by weight.
• the inks may comprise water-miscible organic solvents, for example 01- C4alcohols, e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or iso-butanol; amides, e.g. dimethylformamide or dimethylacetamide; ketones or ketone alcohols, e.g. acetone or diacetone alcohol; ethers, e.g. tetra hydrofuran or dioxane; nitrogen-containing heterocyclic compounds, e.g.
• 01- C4alcohols e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or iso-butanol
• amides e.g. dimethylformamide or dimethylacetamide
• poly-alkylene glycols e.g. polyethylene glycol or polypropylene glycol
• C2 C6alkylene glycols and thio-glycols e.g. ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thio-diglycol, hexylene glycol and diethylene glycol
• other polyols e.g. glycerol or 1,2,6-hexane- triol
• C1-C4alkyl ethers of polyhydric alcohols e.g.
• 2-methoxy-ethanol 2-(2- methoxy-ethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxy- ethoxy)ethoxy]ethanol or 2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2- pyrrolidone, diethylene glycol, glycerol or especially 1,2-propylene glycol, usually in an amount of from 2 to 30 % by weight, especially from 5 to 30 % by weight and preferably from 10 to 25 % by weight, based on the total weight of the ink.
• the inks may also comprise solubilisers, e.g. p-caprolactam.
• the inks may comprise thickeners of natural or synthetic origin, inter alia for the purpose of adjusting the viscosity.
• thickeners examples include commercially available alginate thickeners, starch ethers or locust bean flour ethers, especially sodium alginate on its own or in admixture with modified cellulose, e.g. methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose, especially with preferably from 20 to 25 % by weight carboxymethyl cellulose.
• modified cellulose e.g. methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose, especially with preferably from 20 to 25 % by weight carboxymethyl cellulose.
• Synthetic thickeners that may also be mentioned are, for example, those based on poly(meth)acrylic acids or poly(meth)acrylamides and also polyalkylene glycols having a molecular weight of, for example, from 2000 to 20 000, such as, for example, polyethylene glycol or polypropylene glycol or mixed polyalkylene glycols of ethylene oxide and propylene oxide.
• the inks contain such thickeners, for example, in an amount of from 0.01 to 2 % by weight, especially from 0.01 to 1 % by weight and preferably from 0.01 to 0.5 % by weight, based on the total weight of the ink.
• the inks may also comprise buffer substances, e.g. borax, borates, phosphates, poly-phosphates or citrates.
• buffer substances e.g. borax, borates, phosphates, poly-phosphates or citrates.
• borax e.g. borax, borates, phosphates, poly-phosphates or citrates.
• borax sodium borate, sodium tetraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate and sodium citrate. They are used especially in amounts of from 0.1 to 3 % by weight, preferably from 0.1 to 1 % by weight, based on the total weight of the ink, in order to establish a pH value of, for example, from 4 to 9, especially from 5 to 8.5.
• the inks may comprise surfactants or humectants.
• Suitable surfactants include commercially available anionic or non-ionic surfactants.
• humectants in the inks according to the invention there come into consideration, for example, urea or a mixture of sodium lactate (advantageously in the form of a 50 % to 60 % aqueous solution) and glycerol and/or propylene glycol in amounts of preferably from 0.1 to 30 % by weight, especially from 2 to 30 % by weight.
• the inks may in addition comprise customary additives, e.g. antifoams or especially preservatives that inhibit fungal and/or bacterial growth.
• additives are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the ink.
• formaldehyde-yielding agents for example paraformaldehyde and trioxane, especially aqueous, approximately from 30 to 40 % by weight formaldehyde solutions, imidazole compounds, for example 2- (4-thiazolyl)-benzimidazole, thiazole compounds, for example 1,2-benzisothiazolin-3- one or 2-n-octyl-isothiazolin-3-one, iodine compounds, nitriles, phenols, haloalkylthio compounds or pyridine derivatives, especially 1 ,2-benzisothiazolin-3-one or 2-n-octyl- isothiazolin-3-one.
• a suitable preservative is, for example, a 20 % by weight solution of 1 ,2-benzisothiazolin-3-one in dipropylene glycol (Proxel® GXL).
• the inks may in addition comprise further additives, such as fluorinated polymers or telomers, for example polyethoxyperfluoroalcohols (Forafac® or Zonyl® products) in an amount of, for example, from 0.01 to 1 % by weight, based on the total weight of the ink.
• fluorinated polymers or telomers for example polyethoxyperfluoroalcohols (Forafac® or Zonyl® products) in an amount of, for example, from 0.01 to 1 % by weight, based on the total weight of the ink.
• the ink-jet printing method individual droplets of ink are sprayed onto a substrate from a nozzle in a controlled manner. It is mainly the continuous inkjet method and the drop-on-demand method that are used for that purpose.
• the droplets are produced continuously, droplets not required for the printing operation being discharged into a receptacle and recycled.
• droplets are generated as desired and used for printing; that is to say, droplets are generated only when required for the printing operation.
• the production of the droplets can be effected, for example, by means of a piezo ink-jet head or by thermal energy (bubble jet). Preference is given to printing by means of a piezo ink-jet head and to printing according to the continuous ink-jet method.
• the present invention also concerns the use of at least one reactive dye of formula (I) according to the invention, or a mixture comprising such a dye, or the ink according to the invention, in the dyeing or printing of textile material such as hydroxyl-group-containing or nitrogen-containing fibre material, especially cellulosic fibre material, or in other words, a process for the dyeing or printing of textile material such as hydroxyl-group-containing or nitrogen-containing fibre material, especially cellulosic fibre material, wherein at least one reactive dye of formula (I) according to the invention, or a mixture comprising such a dye, or an ink according to the invention is used.
• the process for dyeing and printing of hydroxy-group-containing or nitrogencontaining fibre materials according to the invention can be carried out in accordance with customary dyeing and printing methods, for example, according to the so-called cold pad-batch process, in which the dye according to the invention, or the dye mixture, or the ink is applied, together with the alkali, on the padder and is then fixed by storage for several hours at about room temperature, for example, from 25 to 35°C.
• the process for dyeing and printing according to the invention can be carried out according to the exhaust-dyeing method, in which the goods are impregnated with aqueous, optionally salt-containing, solution comprising the dye or dye mixture according to the invention, and the dye or the dye mixture is fixed after an alkali treatment or in the presence of alkali, optionally under the action of heat.
• the amounts in which the dye or the dye mixture according to the invention or the ink according to the invention is used for dyeing or for printing can vary within wide limits in dependence upon the desired depth of shade; in general, amounts of from 0.01 to 15% by weight, especially from 0.1 to 10% by weight, based on the goods being dyed or printed, have proved advantageous.
• the present invention also concerns a textile dyed or printed with at least one reactive dye of formula (I) according to the invention, or a dye mixture according to the invention or the aqueous ink according to the invention.
• the dyeings and prints produced using the dye or the dye mixture or the ink according to the invention have a high tinctorial strength and a high fibre-dye binding stability in both the acidic and the alkaline range, are remarkable through their non photochromic character, and also have good light and chlorine fastnesses, good wash-off behaviour, excellent operational excellence (reproductibility, fixing time, etc.)
• step (a2) diazotization of the mixture obtained in step (a1) with a 4N solution of sodium nitrite in slight molar excess (sodium nitrite: mixture obtained in step (a1)) of 1.05-1.1 : 1.0 to ensure complete diazotization, at 0-30°C
• step (a3) the reaction mixture obtained in step (a2) is stirred for one hour and excess of nitrite is neutralized by addition of sulfamic acid 10% solution, thus providing the required diazonium salt.
• the mixture obtained at step (a) is cooled with ice at 0-5°C and at pH 6.0-8.0, and 55.5 g of cyanuric chloride is rapidly (less than 1 min) added to said mixture.
• the pH of said mixture is adjusted and maintained at 5.0-6.0 for one hour at 15-25°C by addition of sodium carbonate 20% solution. After reaction completion, the suspension is at a temperature of 15-25°C and at a pH of 5.0-6.0.
• step (b) 3,5-diaminobenzoic acid solution is added over 5 min to the mixture obtained in step (b) heated at 55 - 65°C.
• the subsequent mixture is heated 55 - 65°C, while the pH is maintained at 4.0 - 4.5 by addition of sodium carbonate 20% solution, the mixture is stirred at 55 - 65°C until reaction completion.
• reaction mass After reaction completion, the reaction mass is cooled to a temperature of 35 - 40°C and unreacted 3,5-diaminobenzoic acid is quenched with drops of acetic anhydride.
• the pH of said reaction mass is then set up at 5.5-6.0 with sodium carbonate 20% solution and the reaction mass is heated up to 30-50°C, submitted to reverse osmosis process and dried leading to the crude reactive dye which main component, in the form of the free acid, corresponds to the formula (101-a):
• Compound (101-b) can be obtained using literature known conditions from compound (101-a)
• the conversion of a vinylatable reactive group -SO2-CH2-CH2- OSO3H into its vinyl form is implemented by treatment with dilute sodium hydroxide solution, such as the conversion of the -sulfatoethylsulfonyl radical into the vinylsulfonyl radical.
• dilute sodium hydroxide solution such as the conversion of the -sulfatoethylsulfonyl radical into the vinylsulfonyl radical.
• Those transformation reactions are generally affected in a neutral to alkaline medium at a temperature of, for example, from 20 to 70°C, at a pH of, for example, from 6 to 14.
• step (a2) diazotization of the mixture obtained in step (a1) with a 4N solution of sodium nitrite in slight molar excess (sodium nitrite: mixture obtained in step (a1)) of 1.05-1.1 : 1.0 to ensure complete diazotization, at 0-30°C
• step (a3) the reaction mixture obtained in step (a2) is stirred for one hour and excess of nitrite is neutralized by addition of sulfamic acid 10% solution, thus providing the required diazonium salt.
• the mixture obtained at step (a) is cooled with ice at 0-5°C and at pH 6.0-8.0, and 55.5 g of cyanuric chloride is rapidly (less than 1 min) added to said mixture.
• the pH of said mixture is adjusted and maintained at 5.0-6.0 for one hour at 15-25°C by addition of sodium carbonate 20% solution. After reaction completion, the suspension is at a temperature of 15-25°C and at a pH of 5.0-6.0.
• 2-amino-4-sulfobenzoic acid solution is added over 5 min to the mixture obtained in step (b) and the mixture is heated to 45-50°C. While the pH is maintained at 4.0 - 4.5 by addition of sodium carbonate 20% solution, the mixture is stirred at 45 - 50°C until reaction completion.
• reaction mass After reaction completion, the reaction mass is cooled to a temperature of 20- 25°C and unreacted 2-amino-4-sulfobenzoic acid is quenched with drops of acetic anhydride.
• the pH of said reaction mass is then set up at 5.0-5.5 with sodium carbonate 20% solution and the reaction mass is heated up to 30-50°C, submitted to reverse osmosis process and dried leading to the crude reactive dye which main component, in the form of the free acid, corresponds to the formula (201-a):
• Compound (201)-b can be obtained using literature known conditions from compound (201-a)
• the conversion of a vinylatable reactive group -SO2-CH2-CH2- OSO3H into its vinyl form is implemented by treatment with dilute sodium hydroxide solution, such as the conversion of the -sulfatoethylsulfonyl radical into the vinylsulfonyl radical.
• dilute sodium hydroxide solution such as the conversion of the -sulfatoethylsulfonyl radical into the vinylsulfonyl radical.
• Those transformation reactions are generally affected in a neutral to alkaline medium at a temperature of, for example, from 20 to 70°C, at a pH of, for example, from 6 to 14.
• This example illustrates different mixes of the compounds (101) with one or more compounds (201) and / or other dyes from the list recited above.
• This example illustrates a mixture of compounds (101 -a) and (201 -a) with a mix (101 -a : 201 -a) of 20:80 molar ratio value.
• This example illustrates a mixture of compounds (101-b) and (201-b) with a mix (101-b : 201-b) of 20 : 80 molar ratio value. It is achieved in a similar manner as described in the example 3-a
• Example 4-a In a similar manner as described in example 3, a mix Ratio of (101-a) : (201-a) as 33 : 66 molar ratio is obtained by mixing 106.7 g of molecule of formula (101-a) and 130.4 g of molecule of formula (201-a).
• This example illustrates a mixture of compounds (101-b) and (201 -b) with a mix (101-b : 201 -b) of 33 : 66 molar ratio value. It is achieved according to a same manner as described in the example 4-a.
• This example illustrates a mixture as 30 : 70 weight ratio value by mixing respectively the corresponding weight of :
• This example illustrates a mixture as 50 : 50 weight ratio value by mixing respectively the corresponding weight of :
• This example illustrates a mixture as 30 : 70 weight ratio value by mixing respectively the corresponding weight of :
• This example illustrates a mixture as 50 : 50 weight ratio value by mixing respectively the corresponding weight of :
• This example illustrates a mixture as 30 : 70 weight ratio value by mixing respectively the corresponding weight of :
• This example illustrates a mixture as 30 : 70 weight ratio value by mixing respectively the corresponding weight of :
• a cotton tricot fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 1:10 which contains the inventive dyebaths AE 1 to AE 4 and reference dyebaths AE5 and AE6, each dyebath being tested at six different concentrations.
• composition of dyebaths AE 1 to AE 6 is prepared in 6 concentrations C1 to C6 described in table 1 below, containing sodium chloride nd amount of either
• % of dyestuff mixture or dyestuff is with respect to the weight of the cotton fabric
• [g/l] refers to grams of salt per litter of solution
• the tinctorial strengths of the dyeings obtained with the dyeing liquors 1 to 6 are measured spectrophotometrically.
• Table 2 shows the build-up properties of the application examples according to the invention AE1 to AE11 and the single dyes of formula R. YE 205 (AE 5) and R. YE. 222 (AE 6) as benchmarks.
• the dyestuff mixtures according to the present invention shows very good build-up properties in comparison to the single dyestuff components.
• a bleached cotton tricot fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 1 :6 which contains 55 g/l of sodium chloride, and
• the washed fabrics are subjected to the following colour fastness tests:
• Table 4 Fastness properties of single dye of dyestuff compound example 1-a
• Table 5 Fastness properties of dyestuff mixture example 4-a
• Table 7 Fastness properties of dyestuff mixture example 7
• Table 8 Fastness properties of single dyestuff of compound of formula R.YE 222 Application Example C
• the washed fabrics obtained in application example A are subjected to the following measurements and fastness tests:

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Coloring (AREA)
• Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=84604075

Family Applications (1)

Country Status (4)

Family Cites Families (2)

• 2023
  • 2023-12-20 EP EP23836509.2A patent/EP4638607A1/de active Pending
  • 2023-12-20 CN CN202380088386.3A patent/CN120418355A/zh active Pending
  • 2023-12-20 WO PCT/EP2023/087123 patent/WO2024133576A1/en not_active Ceased
  • 2023-12-21 AR ARP230103506A patent/AR131468A1/es unknown

Also Published As

Similar Documents

Legal Events