TW201302926A - Fibre-reactive dyes, their preparation and their use - Google Patents

Abstract

Reactive dyes of formula, wherein R1 and R2 are each independently of the other hydrogen or unsubstituted or substituted C1-C4alkyl, one of the radicals D1 and D2 is a radical of the formula, the other one of the radicals D1 and D2 is a radical of the formula, or, wherein (R3)n denotes n identical or different substituents selected from the group C1-C4alkyl, C1-C4alkoxy and sulfo, Z1 is a radical of the formula -SO2-Y (4a), -CONH-(CH2)p-SO2-Y (4b), -NH-CO-CH(Hal)-CH2-Hal (4c), -NH-CO-C(Hal)=CH2 (4d), or, wherein X1 is halogen, T1 independently has the definition of X1, is a non-fibre-reactive substituent or is a fibre-reactive radical of the formula, -NH-(CH2)2-3-SO2-Y (5b), or -NH-(CH2)2-3-O-(CH2)2-3-SO2-Y (5c), R4 is hydrogen or unsubstituted or substituted CrC4alkyl, (R5)0-2 denotes from 0 to 2 identical or different substituents from the group C1-C4alkyl, C1-C4alkoxy and sulfo, Hal is halogen, Y is vinyl or a -CH2-CH2-U radical and U is a group that is removable under alkaline conditions, k is the number 0, 1 or 2, m is the number 2, 3 or 4, n is the number 0, 1 or 2, and p is the number 2, 3 or 4, are suitable for dyeing cellulosic or amide-group-containing fibre materials.

Description

Fiber reactive dye, its preparation and use thereof

The present invention relates to fiber reactive dyes, processes for their preparation and their use for dyeing or printing textile fiber materials.

The recent practice of dyeing with reactive dyes has resulted in higher requirements for the quality of the dyeing and the economics of the dyeing process. Therefore, there is a continuing need for novel reactive dyes which have improved properties, particularly in terms of dye application.

Today's dyeing requires a reactive dye that is sufficiently straightforward and at the same time unfixed, the dye is easily washable. It should also have a good color yield and high reactivity, and the object is particularly to provide a dyeing product having a high degree of fixation. It is known that dyes do not meet these requirements for all properties.

Dyes known from JP-A-08-60017 and US-A-6,537,332 still have certain disadvantages in terms of the properties mentioned above.

A potential problem with the present invention is therefore the discovery of improved novel reactive dyes having the qualities characterized above to a high grade for dyeing and printing fibrous materials. The novel dyes differ in particular by good build-up characteristics, high fixed amounts and high fiber dye binding stability, and additionally dyes that are not fixed to the fibers should be easily washed away. Dyes should also produce dyes with good overall fastness properties such as light fastness and wash fastness.

It has been found that the problems raised are mainly solved by novel dyes as defined below.

The invention therefore relates to reactive dyes of the formula: Wherein R ₁ and R ₂ are each independently hydrogen or unsubstituted or substituted C ₁ -C ₄ alkyl, and one of the groups D ₁ and D ₂ is a group of the formula: The other of the groups D ₁ and D ₂ is a group of the formula: Wherein (R ₃ ) _n represents the same or different substituents selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfo groups, and Z ₁ is a group of the formula:- SO ₂ -Y (4a), -CONH-(CH ₂ ) _p -SO ₂ -Y (4b), -NH-CO-CH(Hal)-CH ₂ -Hal (4c), -NH-CO-C( Hal)=CH ₂ (4d) or Wherein X ₁ is halogen, and T ₁ independently has the definition of X ₁ , is a non-fibrous reactive substituent or is a fiber reactive group of the formula: -NH-(CH ₂ ) _2-3 -SO ₂ -Y (5b) or -NH-(CH ₂ ) _2-3 -O-(CH ₂ ) _2-3 -SO ₂ -Y (5c), R ₄ Is hydrogen or unsubstituted or substituted C ₁ -C ₄ alkyl, (R ₅ ) _0-2 represents 0 to 2 from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfo group The same or different substituents of the group, Hal is a halogen, Y is a vinyl or -CH ₂ -CH ₂ -U group, and U is a group which can be removed under basic conditions, k is a number 0, 1 or 2, m is the number 2, 3 or 4, n is the number 0, 1 or 2, and p is the number 2, 3 or 4.

As C ₁ -C ₄ alkyl, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, The second butyl, isobutyl and tert-butyl groups are especially methyl and ethyl. The alkyl groups R ₁ , R ₂ and R ₄ may be an unsubstituted alkyl group or may be, for example, a hydroxyl group, a sulfo group, a sulfato group, a cyano group, a carboxyl group, a C ₁ -C ₄ alkoxy group or a Phenyl, preferably via hydroxy, sulfo, C ₁ -C ₄ alkoxy or via phenyl, and especially substituted by sulfo.

In a preferred embodiment, one of the groups R ₁ and R ₂ is hydrogen and the other of the groups R ₁ and R ₂ is one or more of the unsubstituted or substituted C ₁ a -C ₄ alkyl group such as a methyl group, an ethyl group or a group of the formula -CH ₂ -SO ₃ H.

In another preferred embodiment, R ₁ and R ₂ are hydrogen.

In another preferred embodiment, R ₁ is hydrogen and R ₂ is hydrogen, methyl or a group of the formula -CH ₂ -SO ₃ H.

R _{4 is} preferably hydrogen or an unsubstituted C ₁ -C ₄ alkyl group such as a methyl group or an ethyl group.

As the C ₁ -C ₄ alkoxy group, it is considered to be, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third group for R ₃ and R _{5 .} Butoxy, preferably methoxy and ethoxy, and especially methoxy.

R ₃ preferably represents the same or different substituents selected from the group consisting of methyl, methoxy and sulfo groups.

(R ₅ ) _0-2 preferably represents 0 to 2 of the same or different substituents selected from the group consisting of methyl, methoxy and sulfo groups.

As the leaving group U, it is considered to be, for example, -Cl, -Br, -F, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OPO ₃ H ₂ , -OCO-C ₆ H ₅ ,- OSO ₂ -C ₁ -C ₄ alkyl and -OSO ₂ -N(C ₁ -C ₄ alkyl) ₂ . U is preferably a group of the formula: -Cl, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OCO-C ₆ H ₅ or -OPO ₃ H ₂ , especially -Cl or -OSO ₃ H.

Thus examples of suitable groups Y are vinyl, β-bromo-ethyl or β-chloro-ethyl, β-ethoxycarbonyl-ethyl, β-benzyloxyethyl, β-phosphonium oxide Base ethyl, β-sulfatoethyl and β-thiosulfatoethyl.

Y is preferably independently a vinyl group, a β-chloroethyl group or a β-sulfatoethyl group.

k is preferably a number 1 or 2.

m and p are preferably each independently of the number 2 or 3.

m is particularly preferably a number 3.

n is preferably a number of 0 or 1.

p is particularly preferably the number 2.

Z _{1 is} preferably a group of the formula (4a), the formula (4b) or the formula (4e), especially a group of the formula (4a) or the formula (4e), and more particularly a group of the formula (4a), These variables have the definitions and preferred meanings given above.

In a preferred embodiment, D ₁ corresponds to a group of formula (2) and D ₂ corresponds to a group of formula (3a) or formula (3b), wherein R ₃ , Z ₁ , Y, k, m and n each have the definitions given above and preferred meanings.

In a particular embodiment, D ₂ corresponds to a group of formula (3a), wherein R ₃ , Z ₁ and n each have the definitions given above and preferred meanings.

In a particularly preferred embodiment, D ₂ is a group of the formula: Wherein Y is a vinyl group or a β-sulfate root.

T ₁ when a non-fiber-reactive substituents, which may be, for example, hydroxy; C ₁ -C ₄ alkoxy; unsubstituted or substituted, for example, the hydroxyl, carboxyl or sulfo C ₁ -C ₄ alkylthio An amine group; a mono- or di-substituted amine group via a C ₁ -C ₈ alkyl group, wherein the alkyl group itself may be, for example, a sulfo group, a sulfate group, a hydroxyl group, a carboxyl group or a phenyl group, especially a sulfo group or Substituted by a hydroxy group and may be heteroatomically one or more times via a group -O-; cyclohexylamino; morpholinyl; NC ₁ -C ₄ alkyl-N-anilino, anilino or naphthylamino, wherein the benzene Or a naphthyl group which is unsubstituted or substituted with, for example, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₂ -C ₄ alkylalkylamino group, a carboxyl group, a sulfo group or a halogen group, and the alkyl group Unsubstituted or substituted with, for example, a hydroxyl group, a sulfo group or a sulfate group.

Examples of suitable non-fibrous reactive substituents T ₁ are amine, methylamino, ethylamine, β-hydroxyethylamino, N-methyl-N-β-hydroxyethylamino, N-ethyl-N -β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino, morpholinyl, 2-chloroanilino, 3-chloroanilino or 4-chloroanilino, 2-methylanilino, 3-methylanilino or 4-methylanilino, 2-methoxyanilino, 3-methoxyanilino or 4-methoxyanilino , 2-sulfoanilino, 3-sulfoanilino or 4-sulfoanilino, 2,5-disulfoanilino, 2-carboxyanilino, 3-carboxyanilino or 4-carboxyanilino, 1-naphthylamino or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenyl-amino, N-methyl-N-anilino, methoxy, ethoxy, n-propoxy or isopropoxy and hydroxy.

As a non-fiber-reactive substituent, T ₁ is preferably C ₁ -C ₄ alkoxy; unsubstituted or substituted with hydroxyl, carboxyl or substituted by a sulfo group of C ₁ -C ₄ alkylthio group; a hydroxyl group; amine Unsubstituted or N-mono-C ₁ -C ₄ alkylamino group or N,N-di-C ₁ - substituted by a hydroxyl group, a sulfate group or a sulfo group in one or more alkyl moieties C ₄ alkylamino; morpholinyl; an anilino group which is unsubstituted or substituted with a sulfo group, a carboxyl group, an acetamino group, a chlorine group, a methyl group or a methoxy group on a benzene ring; or NC ₁ - C ₄ An alkyl-N-anilinyl group which is unsubstituted or substituted on the phenyl ring in the same manner as the anilino group and wherein the alkyl group is unsubstituted or substituted with a hydroxyl group, a sulfo group or a sulfate group; or Naphthylamino group substituted or substituted with 1 to 3 sulfo groups.

Particularly preferred non-fibrous reactive substituents T ₁ are an amine group, an N-methylamino group, an N-ethylamino group, an N-β-hydroxyethylamino group, an N-methyl-N-β-hydroxyethylamino group, N-ethyl-N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, morpholinyl, 2-carboxyanilino, 3-carboxyanilinyl Or 4-carboxyanilino, 2-sulfoanilino, 3-sulfoanilino or 4-sulfoanilino, 2,5-disulfoanilino and NC ₁ -C ₄ alkyl-N-anilino .

X ₁ is, for example, fluorine, chlorine or bromine, especially fluorine or chlorine.

Hal is, for example, chlorine or bromine, especially bromine.

T _{1 is} preferably a fiber-reactive group of the formula (5a), and the variables have the definitions given above and preferred meanings.

A preferred specific example of the present invention based on formula (1) of the reactive dye, wherein R ₁ is hydrogen, R ₂ is hydrogen, methyl or a group of formula -CH ₂ -SO ₃ H's.

D ₁ corresponds to the group of the formula (2) and D ₂ corresponds to the group of the formula (3a), and the variables have the definitions given above and preferred meanings; preferably, R ₃ represents n selected from the group A The group, the methoxy group and the sulfo group are preferably selected from the same or different substituents of the group of sulfo groups, Z ₁ is a group of the formula (4a) as defined above, and Y is a vinyl group, β-chloroethane Or a β-sulfate complex ethyl group, k is a number 1 or 2, m is a number 2 or 3, preferably 3, and n is a number 0, 1 or 2, preferably a number 0 or 1.

A particularly preferred embodiment of the invention relates to a reactive dye of formula (1) wherein R ₁ is hydrogen and R ₂ is hydrogen, methyl or a group of the formula -CH ₂ -SO ₃ H.

D ₁ corresponds to a group of the formula (2), wherein Y is a vinyl group or a β-chloroethyl group, k is a number 1 or 2, m is a number 3, and D ₂ is a formula (3aa) as defined above Group.

The invention also relates to a process for the preparation of a dye of formula (1) which comprises (i) diazotizing an amine of the formula: D ₂ -NH ₂ (6) in a conventional manner, and The coupling reaction of the compound of the formula below about 1 molar equivalent (first coupling reaction): Forming a compound of the formula: And (ii) diazotizing about 1 molar equivalent of the amine of the formula: D ₁ -NH ₂ (9), and having about 1 mole equivalent of the compound of formula (8a) obtained according to (i) The coupling reaction is carried out to form a compound of the formula (1) (second coupling reaction), wherein D ₁ , D ₂ , R ₁ and R ₂ each have the definitions given above and preferred meanings.

The amines of the formulae (6) and (9) are subjected to diazotization in a manner known per se, for example at a temperature of, for example, -5 ° C to 40 ° C and preferably 0 ° C to 20 ° C in a mineral acid medium, for example In a hydrochloric acid medium, a nitrite such as an alkali metal nitrite such as sodium nitrite is used.

In an acidic or neutral to weakly alkaline pH, for example at a pH of from 0 to 8, and at a temperature of, for example, -5 ° C to 40 ° C, preferably 0 ° C to 30 ° C, in a manner known per se and formula (7) The coupling component of the formula (8a) is coupled.

The first coupling reaction (i) is carried out in an acidic medium, for example at a pH of 0 to 4, and the second coupling reaction (ii) is at a raised pH, in a weakly acidic, neutral or weakly basic medium. It is carried out, for example, at a pH of 4 to 8.

By carrying out as described above, but in process steps (i) and (ii), at least two of about 1 molar equivalents, preferably a mixture of two different amines, for example, formula (6), are used in each case. a 1:1 molar mixture of the compound and the compound of the formula (9), instead of using about 1 molar equivalent of each of the amines of the formula (6) and the formula (9), first obtaining the following formula according to (i) Mixture of compounds: And after further reacting the compound of the formula (8a) with the compound of the formula (8b) according to (ii), a mixture of the dyes of the formula (1), the formula (1b), the formula (1c) and the formula (1d) is obtained:

The invention therefore also relates to a dye mixture comprising at least one dye of the formula (1) and formula (1b) and at least one dye of the formula (1c) and the formula (1d), in particular comprising the formula (1), formula (1b) And a dye of each of formula (1c) and formula (1d), wherein D ₁ , D ₂ , R ₁ and R ₂ each have the definitions given above and preferred meanings.

The ratio of the dyes of the formula (1), the formula (1b), the formula (1c) and the formula (1d) in the mixture can be varied within a wide range and depending on the specific amine D ₁ -NH ₂ used in accordance with (i) and (ii) It depends on the ratio of D ₂ -NH ₂ .

The above dye mixture contains, for example, from 5% by weight to 95% by weight, especially from 10% by weight to 90% by weight, based on the total of the dyes of the formula (1), the formula (1b), the formula (1c) and the formula (1d). A dye of the formula (1) and/or the formula (1b) is preferably from 20% by weight to 80% by weight.

The compounds of the formula (6), the formula (7) and the formula (9) are known or can be obtained in a manner known per se.

For example, a compound of formula (6) wherein D ₂ is a group of the above formula (3a) and Z _{1 is} within the meaning of the group of formula (4e) can be at a pH within the neutral range and is, for example, About 1 molar equivalent of 2,4,6-trichloro-all three at a low temperature of 0 ° C to 5 ° C Or 2,4,6-trifluoro-all three It is first prepared by condensation with about 1 mole equivalent of the compound below: T ₁ -H (10).

Such condensation reactions are known and are described, for example, in EP-A-0 260 227 and US-A-4 841 049.

Some of the compounds of formula (9) are novel compounds. Accordingly, the present invention is also directed to compounds of the formula: Wherein Y is a vinyl or -CH ₂ -CH ₂ -U group, and U is a group which can be removed under basic conditions, k is the number 2, and m is the number 3, wherein Y has the above given Definition and preferred meaning.

The preparation of the compound of formula (11) is described in the experimental section.

A reactive dye of the formula (1) of the present invention, a dye mixture comprising at least one dye of the formula (1) and the formula (1b), and at least one dye of the formula (1c) and the formula (1d), and a compound of the formula (11) It is in the form of a free acid or preferably in the form of its salt. Salts contemplated are, for example, alkali metal salts, alkaline earth metal salts and salts of ammonium salts and organic amines. Sodium, lithium, potassium and ammonium salts and salts of monoethanolamine, diethanolamine or triethanolamine may be mentioned as examples.

The final product can also undergo a conversion reaction where appropriate. The conversion reaction is, for example, conversion of the vinylatable reactive group contained in Z ₁ or Y to its vinyl form by treatment with a dilute sodium hydroxide solution, for example, β-sulfate ethyl sulfonyl group Or converting the β-chloroethylsulfonyl group to a vinylsulfonyl group or converting the α,β-dihalopropylamino group to an α-halopropenylamine group. These reactions are known per se. The conversion reaction is generally carried out in a neutral to basic medium at a temperature of, for example, 20 ° C to 70 ° C, for example, at a pH of 6 to 14.

The dyes and dye mixtures of the invention are fiber reactive. A fiber-reactive dye is understood to be capable of reacting with a hydroxyl group of cellulose, with an amine group, a carboxyl group, a hydroxyl group or a thiol group in the wool and silk, or with an amine group of a synthetic polyamine and a carboxyl group which may be present to form a covalent chemical bond. Fiber reactive dye.

The dyes and dye mixtures of the invention are suitable for a very wide range of materials Dyeing and printing, such as hydroxyl-containing fibrous materials or nitrogen-containing fibrous materials. Examples are silk, leather, wool, polyamide fibers and polyurethanes and especially all types of cellulosic fiber materials. Such cellulosic fibrous materials are, for example, natural cellulosic fibers such as cotton, linen and hemp fibers, as well as cellulose and regenerated cellulose. The dyes and dye mixtures of the present invention are also suitable for dyeing or printing hydroxy-containing fibers present in blended fabrics such as cotton and polyester fibers or polyamide fibers. The dyes and dye mixtures of the invention are especially suitable for dyeing or printing cellulosic fibrous materials, especially cotton-containing fibrous materials. It can also be used to dye or print natural or synthetic polyamide fibers.

The dyes and dye mixtures of the present invention can be applied to the fibrous material and to the fibers in a variety of ways, particularly in the form of aqueous dye solutions and dye printing pastes. It is suitable for the dip dyeing process and is suitable for dyeing according to the padding process, according to the above process, the article is impregnated with the salt aqueous dye solution according to the condition, and after the treatment with alkali or in the presence of a base, as the case may be under heating or The dye is fixed by holding it at room temperature for several hours. After fixation, the dyed product or print is suitably rinsed with cold water and hot water, optionally with the addition of a dispersing agent that promotes the diffusion of the unfixed dye.

The dyes and dye mixtures of the present invention are used in the absence of high reactivity, good fixing ability and excellent lifting ability. It can therefore be used to carry out the dip dyeing process at low dyeing temperatures, and only requires a short steaming time in the pad dyeing steaming process. The high degree of fixation and the unfixed dye can be easily washed away, and the difference between the degree of impregnation and the degree of fixation is remarkably small, that is, the soaping loss is extremely small. The dyes and dye mixtures of the invention are also particularly suitable for printing, more particularly for Cotton is printed and is also suitable for printing on nitrogen-containing fibers such as wool or silk or blended fabrics containing wool or silk.

Dyes and prints produced by using the dye of the present invention have high color strength and high fiber dye combination stability in the acidic and alkaline range, as well as good light fastness and excellent wet fastness properties, such as washable, water resistant, Water-resistant, cross-dyeing and perspiration fastness, as well as good pleating resistance, heat resistance and rubbing fastness.

The reactive dye of the formula (1) of the present invention and the dye mixture comprising at least one dye of the formula (1) and the formula (1b) and at least one dye of the formula (1c) and the formula (1d) are preferably combined with other reactive dyes. Applications such as navy, dark blue or black dyes (such as CI Reactive Black 5), or dyes as described in US-A-4,622,390, US-A-6,458,936 and WO 2004/088031 (Formula (102), (104), Formula (105), Formula (106), and Dye of Formula (107), which are incorporated herein by reference.

The present invention is also directed to an aqueous ink comprising a reactive dye of formula (1), the respective definitions and preferred meanings given above being applicable to D ₁ , D ₂ , R ₁ and R ₂ .

The dye used in the ink should preferably have a low salt content, i.e., the total salt content should be less than 0.5% by weight based on the weight of the dye. Dyes having a relatively high salt content due to preparation and/or subsequent addition of a diluent can be desalted, for example, by a membrane separation procedure such as ultrafiltration, reverse osmosis or dialysis.

The total dye content of the ink is preferably from 1% by weight to 35% by weight, particularly from 1% by weight to 30% by weight, and preferably from 1% by weight to 20% by weight, based on the total weight of the ink. As a lower limit, a limit of 1.5% by weight, preferably 2% by weight and especially 3% by weight is preferred.

The ink may comprise a water-miscible organic solvent such as a C ₁ -C ₄ alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol and isobutanol; Amines such as dimethylformamide and dimethylacetamide; ketones or ketols such as acetone and diacetone; ethers such as tetrahydrofuran and dioxane; nitrogen-containing heterocyclic compounds such as N-methyl- 2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; C ₂ -C ₆ alkylene glycol and thioglycol, for example Ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexanediol and diethylene glycol; other polyols such as glycerin and 1,2,6-hexanetriol; and polyol a C ₁ -C ₄ alkyl ether such as 2-methoxy-ethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[ 2-(2-methoxyethoxy)-ethoxy]ethanol and 2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2- Pyrrolidone, diethylene glycol, glycerol, or especially 1,2-propanediol, usually in an amount of from 2% by weight to 30% by weight based on the total weight of the ink %, especially 5% by weight to 30% by weight, and preferably 10% by weight to 25% by weight.

The ink may also contain a solubilizing agent such as ε-caprolactam.

In particular, for the purpose of adjusting the viscosity, the ink may comprise a thickener of natural or synthetic origin.

Examples of thickeners which may be mentioned include commercially available alginate thickeners, starch ethers or locust bean powder ethers, especially sodium alginate, alone or mixed with modified cellulose, which are modified cellulose. For example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose, especially preferably 20 5% by weight to 25% by weight of sodium alginate mixed with carboxymethylcellulose. Can be mentioned The thickening agent is, for example, a thickener based on poly(meth)acrylic acid or poly(meth)acrylamide.

The amount of such thickeners contained in the ink is, for example, from 0.01% by weight to 2% by weight, particularly from 0.01% by weight to 1% by weight, and preferably from 0.01% by weight to 0.5% by weight, based on the total weight of the ink.

The ink may also contain a buffer material such as borax, borate, phosphate, polyphosphate or citrate. Examples which may be mentioned include borax, sodium borate, sodium tetraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate and sodium citrate. It is used in an amount of, for example, 0.1% by weight to 3% by weight, based on the total weight of the ink, preferably 0.1% by weight to 1% by weight, to establish a pH of, for example, 4 to 9, especially 5 to 8.5.

As other additives, the ink may comprise a surfactant or a humectant.

Suitable surfactants include commercially available anionic or nonionic surfactants. As a humectant in the ink of the present invention, for example, a mixture of urea or sodium lactate (preferably in the form of a 50% to 60% aqueous solution) and glycerin and/or propylene glycol is considered, and the amount of the humectant is preferably from 0.1% by weight to 30% by weight. Especially from 2% by weight to 30% by weight.

The ink preferably has 1 mPa. s to 40 mPa. s, especially 1 mPa. s to 20 mPa. s and preferably 1 mPa. s to 10 mPa. s viscosity.

The ink may also contain customary additives such as antifoaming agents or, in particular, substances which inhibit the growth of fungi and/or bacteria. These additives are usually used in an amount of from 0.01% by weight to 1% by weight based on the total weight of the ink.

The ink can be prepared in a conventional manner by mixing the individual components together in the desired amount of water.

The inks of the present invention are particularly useful in a recording system in which ink is extruded as small droplets from a small opening and directed onto a substrate on which the image is produced. Suitable substrates are, for example, paper, textile fiber materials or plastic films. Suitable recording systems are, for example, ink jet printers or writing instruments commercially available for printing on paper or textile, such as fountain pens or ballpoint pens, and especially ink jet printers.

Depending on the nature of the application, it may be desirable to modify, for example, the viscosity or other physical properties of the ink, particularly the properties of the affinity to the relevant substrate, as appropriate.

As examples of papers which can be printed with the ink of the present invention, mention may be made of commercially available ink jet paper, photographic paper, glazed paper, plastic coated paper, such as Epson inkjet paper, Epson photographic paper, Epson glaze paper, Epson glaze film, HP-specific Inkjet paper, Encad glossy photo paper and Ilford photo paper. The plastic film which can be printed with the ink of the present invention is, for example, a transparent or turbid/opaque plastic film. A suitable plastic film is, for example, a 3M transparent film.

As the textile fiber material, for example, a nitrogen-containing fiber material or a hydroxy-containing fiber material such as cellulose, silk, wool or synthetic polyamide fiber textile material, preferably a cellulose textile fiber material, is considered.

The invention is therefore also directed to a method for printing textile fiber materials, paper or plastic films, preferably textile fiber materials or paper, and in particular textile fiber materials, by ink jet printing, wherein a reactive dye comprising formula (1) is used. For aqueous inks, the individual definitions and preferred meanings given above apply to D ₁ , D ₂ , R ₁ and R ₂ .

In an inkjet printing process, individual droplets of ink are sprayed onto the substrate in a controlled manner from a nozzle. To achieve this, a continuous ink jet method and a drop-on-demand method are mainly used. Continuous inkjet method Medium, continuously generating small droplets and conveying any small droplets not required for printing into the collecting tank and recycling, and in the on-demand ink dropping method, small droplets are generated as needed and printed; that is, only when printing Small droplets are produced when needed. The droplets can be produced, for example, by means of a piezo inkjet head or by means of thermal energy (bubble inkjet). Printing is preferably carried out by means of a piezoelectric ink jet head of the method of the invention. Additionally, it is preferred to print according to the continuous ink jet method of the method of the present invention.

The resulting records (e.g., prints) differ in particular by high chroma and high color brightness as well as good light fastness and wet fastness characteristics.

The following examples are intended to illustrate the invention. Unless otherwise indicated, temperatures are given in degrees Celsius, parts are parts by weight, and percentages are by weight. The relationship between the parts by weight and the parts by volume is expressed in terms of the ratio of kilograms to liters.

Example 1:

80.5 g of 1,3-phenylenediamine-4,6-disulfonic acid was dissolved in 300 ml of water by means of 60 ml of aqueous sodium hydroxide (30%) at pH 6 to 7. Subsequently, water was added to adjust the volume of the mixture to 500 ml. 250 g of crushed ice was introduced, and 189 g of 4-(2-chloroethylsulfonyl)-butylphosphonium chloride was slowly added while vigorously stirring the mixture. During the addition, the temperature and pH of the reaction mixture were maintained at 0 °C to 3 °C and pH 5 by means of crushed ice and aqueous soda (20% solution).

After the reaction is completed, the insoluble portion is removed by filtration. The obtained solution was adjusted to pH 1.5 by means of hydrochloric acid (32%). Sodium chloride was added under agitation to precipitate the product. The precipitate was separated and suspended in water. An aqueous solution of soda (20%) was added to dissolve the precipitate at pH 4. The obtained solution was adjusted to pH 1.5 by means of hydrochloric acid (32%). Sodium chloride was added under agitation to precipitate the product. The precipitate was separated and suspended in water. An aqueous solution of soda (20%) was added to dissolve the precipitate at pH 6.5. The solution contains a compound in the form of a free acid corresponding to the following formula as a main product:

Example 2:

80.5 g of 1,4-phenylenediamine-2,6-disulfonic acid was dissolved in 300 ml of water at about pH 7 by means of 30 ml of aqueous sodium hydroxide (30%). The volume of the mixture was adjusted to 400 ml by adding water. 300 g of crushed ice was introduced, and 82 g of 4-(2-chloroethylsulfonyl)-butylphosphonium chloride was gradually added while vigorously stirring the mixture, and the pH was maintained at 7.0 with a soda aqueous solution (20% solution). During the addition, the temperature of the reaction mixture was maintained at 0 ° C to 5 ° C by means of crushed ice. After the reaction was completed, water was added to increase the volume of the mixture to 900 ml. The insoluble portion was separated by filtration. The solution contains a compound in the form of a free acid corresponding to the following formula as a main product:

Example 3:

161 by means of 120 ml of aqueous sodium hydroxide (30%) at pH 7. g 1,4-phenylenediamine-2,5-disulfonic acid was dissolved in 800 ml of water. Subsequently, 1000 g of crushed ice was added and the mixture was adjusted to pH 4.8 by the addition of 20 ml of hydrochloric acid (32%). Then, 245 g of 4-(2-chloroethylsulfonyl)-butylphosphonium chloride was slowly added while vigorously stirring the mixture. During the addition, the temperature and pH of the reaction mixture were maintained at 0 °C to 10 °C and pH 5 by means of crushed ice and aqueous soda (20% solution).

After the reaction was completed, the insoluble portion was separated by Dicalite filtration at about 10 °C. The solution contains a compound in the form of a free acid corresponding to the following formula as a main product:

The product can be isolated by dialysis solution to remove salts and then concentrated by evaporation in vacuo.

Example 4:

(a) Diazotization: 704 g of the solution obtained according to Example 1 was cooled to 10 ° C and acidified with 15 ml of hydrochloric acid (32%). 12.5 ml of 4 N sodium nitrite solution was added to the resulting solution at 10 °C. The reaction mixture was stirred for 30 minutes and excess nitrite was eliminated by the addition of amine sulfonic acid. A yellow suspension was obtained.

(b) Second coupling: 2.5 g of disodium hydrogen phosphate was introduced into 385 g of an aqueous solution containing about 30.6 g of the compound of the formula:

The temperature of the solution was adjusted to 5 ° C, and the yellow suspension obtained according to the above step (a) was slowly added while maintaining the mixture at pH 5 by adding a soda aqueous solution (20% solution). When the coupling is completed, the dye solution is salt-free by dialysis and concentrated by vacuum evaporation to obtain a product which mainly contains a compound in a free acid form corresponding to the following formula: (λ _max : 502 nm) and the cellulose was dyed into a red hue with good overall characteristics.

The compound of the formula (104) can be obtained according to the method described in Example 21 of US-A-7,572,301 or Example 26 of US-A-6,537,332 (first coupling reaction). Similar to the method described in US-A-7,572,301 and US-A-6,537,332 (first coupling reaction), a compound similar to the compound of formula (104) is obtained. Monoazo compounds within the scope of the invention.

Example 5:

(a) Diazotization: 382.6 g of the solution obtained according to Example 2 was cooled to 10 ° C and acidified with 28 ml of hydrochloric acid (32%). 25 ml of 4 N sodium nitrite solution was added to the resulting solution at 10 °C. The reaction mixture was stirred for 30 minutes and excess nitrite was eliminated by the addition of amine sulfonic acid. A yellow suspension was obtained.

(b) Second coupling: 20 g of an aqueous solution of disodium hydrogen phosphate (25%) was added to the yellow suspension obtained according to the step (a) at a temperature of 5 °C. To this stirred and cooled suspension was slowly introduced 769.3 g of an aqueous solution containing about 61.2 g of the compound of formula (104) while maintaining the reaction mixture at pH 5 by the addition of a soda aqueous solution (20% solution). Coupling was accomplished by continuing agitation and successively raising the pH of the reaction mixture to pH 7.5 by further addition of a soda aqueous solution (20% solution). Subsequently, the obtained dye solution is adjusted to pH 6, which is salt-free by dialysis and concentrated by vacuum evaporation to obtain a product mainly containing a compound in a free acid form corresponding to the following formula: (λ _max : 490 nm) and cellulose is dyed into a reddish-brown tone with good overall properties.

Example 6

(a) Diazotization: 218.2 g of the amine of the formula:

The suspension was suspended in 500 ml of water and the volume of the suspension was adjusted to 2800 ml by further addition of water. 196 g of sodium chloride were added and the mixture was acidified with 121 ml of hydrochloric acid (32%). 136 ml of 4 N sodium nitrite solution was added to the resulting solution over 45 minutes at room temperature. The suspension obtained was stirred until the reaction was completed, and excess nitrite was eliminated by the addition of amine sulfonic acid.

(b) Second coupling: 3645 g of an aqueous solution containing about 318 g of the compound of the formula (104) was adjusted to pH 6.5 by adding an aqueous solution of soda (20% solution). 3192 g of the suspension obtained according to the above step (a) was slowly added while maintaining the mixture at pH 6.5 by adding a soda aqueous solution (20% solution). Complete the coupling overnight. The reaction mixture was adjusted to pH 5.5 by means of hydrochloric acid (32%). Subsequently, the dye solution is salt-free by dialysis and concentrated by vacuum evaporation to obtain a product which mainly contains a compound in the form of a free acid corresponding to the formula: (λ _max : 506 nm) and the cellulose was dyed into a red hue with good overall characteristics.

Example 7

(a) Diazotization: 26.3 g of the isolated product obtained according to Example 3 was suspended in 200 ml of water. The mixture was acidified with 10 ml of hydrochloric acid (32%). 8.2 ml of a 4 N sodium nitrite solution was added to the resulting solution over 40 minutes at a temperature of 15 ° C to 25 ° C. The suspension obtained was stirred until the reaction was completed, and excess nitrite was eliminated by the addition of amine sulfonic acid.

(b) Second coupling: 298 g of an aqueous solution containing about 20.1 g of the compound of the formula (104) was adjusted to pH 6.5 by adding an aqueous solution of soda (20% solution). The suspension obtained according to the above step (a) was slowly added while maintaining the mixture at pH 6.5 to 7.5 by adding a soda aqueous solution (20% solution). The reaction mixture was adjusted to pH 5.5 by means of hydrochloric acid (32%) and coupled overnight. Subsequently, the dye solution was salt-free by dialysis and concentrated by vacuum evaporation to obtain 50.2 g of a product which mainly contained a compound in a free acid form corresponding to the formula: (λ _max : 514 nm) and cellulose is dyed into a red hue with good overall characteristics.

Example 8

(a) Diazotization: 9.6 g of the amine of the formula:

The suspension was suspended in 100 ml of water and the volume of the suspension was adjusted to 125 ml by further addition of water. 8.8 g of sodium chloride was added and the mixture was acidified with 5.4 ml of hydrochloric acid (32%). 6.2 ml of 4 N sodium nitrite solution was added to the resulting solution over 45 minutes at room temperature. The suspension obtained was stirred until the reaction was completed, and excess nitrite was eliminated by the addition of amine sulfonic acid.

(b) Second coupling: 183 g of the suspension obtained according to the above step (a) was added to 193 g of an aqueous solution containing about 12.2 g of the compound of the formula (104), and by adding an aqueous solution of soda (20% solution) The mixture was adjusted to pH 7.5. After completion of the coupling reaction, the reaction mixture was adjusted to pH 5.5 by means of hydrochloric acid (32%). Subsequently, the dye solution was salt-free by dialysis and concentrated by vacuum evaporation to obtain 23.7 g of a product mainly containing a compound in a free acid form corresponding to the formula: (λ _max : 522 nm) and cellulose is dyed into a red hue with good overall characteristics.

Example 9 to Example 35: Following procedures similar to those described in one of Examples 4 to 8, but using an equimolar amount of an amine of the formula D _{2 xy} -NH ₂ for the first coupling reaction and for the first The di-coupling reaction uses another molar amount of another amine of the formula D 1 _xy -NH ₂ and, as the case may be, 2-methylamino-5-naphthol-7-sulfonic acid or 2-sulfomethylamino-5 -Naphthol-7-sulfonic acid instead of 2-amino-5-naphthol-7-sulfonic acid, obtaining a compound in a free acid form corresponding to the formula (112), wherein D _1xy , D _2xy and R ₂ have The meanings shown in Table 1, Table 2 and Table 3.

Dip dyeing: The dyed cotton fabric was introduced into an aqueous dye bath solution having a ratio of 1:10 at 60 ° C, and the dye bath aqueous solution contained the dye of the formula (108) prepared according to Example 6 in an amount as shown in Table 4. Or reference dye of the following formula: And sodium chloride.

After 45 minutes at 60 ° C, a given amount of calcined sodium carbonate in Table 4 was added. Continue staining for 45 minutes. The dyed article is then rinsed with water, soaped and rinsed again, and then dried.

The coloring intensity of the dyed product obtained from the dyeing liquids 1 to 6 was measured spectrally. Table 5 shows the lifting characteristics of the dye prepared according to Example 6 and the reference dye of formula (201). The dyes of the present invention exhibit excellent lifting characteristics.

Color fastness test for bleached warp knitted fabric dyed with 0.8% dye of formula (108) (reference depth: 0.92) or 1.8% reference dye of formula (201) (reference depth: 0.96) according to the above method ( Xenon arc fading test: 72 hours of irradiation). The color change is determined according to the gray scale. Using the formula (108) of the present invention The dye-dyed fabric was rated 4 to 5, while the fabric dyed with the reference dye of formula (201) was rated only 3 to 4.

Dyeing procedure I

100 parts of cotton fabric was introduced into 1500 parts of a dye bath containing 45 g/l of sodium chloride and 2 parts of the reactive dye obtained according to Example 6 at 60 °C. After 45 minutes at 60 ° C, 20 g/l of anhydrous sodium carbonate was added. The dyeing was continued for another 45 minutes at the temperature. The dyed article is then rinsed, soaped with a non-ionic detergent at the boiling point for a quarter of an hour, rinsed and dried.

As an alternative to the above procedure, dyeing can be carried out at 80 ° C instead of 60 ° C.

Dyeing procedure II

0.1 part of the dye of Example 6 was dissolved in 200 parts of water, and 0.5 part of sodium sulfate, 0.1 part of a leveling adjuvant (based on a condensation product of a higher aliphatic amine and ethylene oxide), and 0.5 part of sodium acetate were added. The pH was then adjusted to a value of 5.5 using acetic acid (80%). The dye bath was heated at 50 ° C for 10 minutes and then 10 parts of wool fabric was added. It was then heated to a temperature of 100 ° C over about 50 minutes and dyed at the temperature for 60 minutes, after which the dye bath was cooled to 90 ° C and the dyed articles were removed. The wool fabric was washed with hot and cold water and then centrifuged and dried.

Printing procedure I

3 parts of the dye obtained according to Example 6 were sprayed in 100 parts containing 50 parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 under rapid stirring. In the original slurry of sodium bicarbonate. Printing the cotton fabric with the printing paste thus obtained, and drying the resulting printing material and Steamed in saturated steam at 102 ° C for 2 minutes. The printed fabric is then rinsed, if necessary, soaped at the boiling point and rinsed again, and then dried.

Printing procedure II

(a) Silk-dyed satin (liquid absorption rate 70%) was padded using a liquid containing 30 g/l sodium carbonate and 50 g/l urea and dried.

(b) printing the cotton satin pre-treated according to the step (a) with an on-demand ink jet head (bubble ink jet) using an aqueous ink containing

- 15% by weight of the reactive dye of the formula (108) of Example 6

- 15% by weight of 1,2-propanediol and

- 70% by weight of water.

The blot was completely dried and fixed in saturated steam for 8 minutes at 102 ° C, cold rinsed, washed at the boiling point, rinsed again and dried.

Claims (11)

A reactive dye of the formula: Wherein R ₁ and R ₂ are each independently hydrogen or unsubstituted or substituted C ₁ -C ₄ alkyl, and one of the groups D ₁ and D ₂ is a group of the formula: The other of the group D ₁ and the group D ₂ is a group of the formula: Wherein (R ₃ ) _n represents the same or different substituents selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfo groups, and Z ₁ is a group of the formula:- SO ₂ -Y (4a), -CONH-(CH ₂ ) _p -SO ₂ -Y (4b), -NH-CO-CH(Hal)-CH ₂ -Hal (4c), -NH-CO-C( Hal)=CH ₂ (4d) or Wherein X ₁ is halogen, and T ₁ independently has the definition of X ₁ , is a non-fibrous reactive substituent or is a fiber reactive group of the formula: -NH-(CH ₂ ) _2-3 -SO ₂ -Y (5b) or -NH-(CH ₂ ) _2-3 -O-(CH ₂ ) _2-3 -SO ₂ -Y (5c), R ₄ Is hydrogen or unsubstituted or substituted C ₁ -C ₄ alkyl, (R ₅ ) _0-2 represents 0 to 2 from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfo group The same or different substituents of the group, Hal is a halogen, Y is a vinyl or -CH ₂ -CH ₂ -U group, and U is a group which can be removed under basic conditions, k is a number 0, 1 or 2, m is the number 2, 3 or 4, n is the number 0, 1 or 2, and p is the number 2, 3 or 4. A reactive dye according to claim 1, wherein R ₁ is hydrogen and R ₂ is hydrogen, methyl or a group of the formula -CH ₂ -SO ₃ H. A reactive dye according to claim 1 or 2, wherein U is -Cl, -Br, -F, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OPO ₃ H ₂ , -OCO-C ₆ H ₅ , -OSO ₂ -C ₁ -C ₄ alkyl or -OSO ₂ -N(C ₁ -C ₄ alkyl) ₂ , preferably -Cl or -OSO ₃ H. A reactive dye according to claim 1 or 2, wherein D ₁ corresponds to a group of the formula: D ₂ corresponds to a group of the formula: Wherein R ₃ , Z ₁ , Y, k, m and n each have the definitions as given in item 1 of the scope of the patent application. A reactive dye according to claim 1, wherein R ₁ is hydrogen, R ₂ is hydrogen, methyl or a group of the formula -CH ₂ -SO ₃ H, and D ₁ corresponds to a group of the formula: D ₂ corresponds to a group of the formula: Wherein R ₃ represents n groups selected from the group consisting of methyl, methoxy and sulfo groups, preferably selected from the same or different substituents of the group of sulfo groups, and Z ₁ is a group of the formula: -SO ₂ -Y ( 4a), Y is a vinyl group, a β-chloroethyl group or a β-sulfatoethyl group, k is a number 1 or 2, m is a number 2 or 3, preferably 3, and n is a number 0, 1 or 2, preferably the number 0 or 1. A process for the preparation of a dye of the formula (1) according to claim 1 which comprises (i) diazotizing an amine of the formula: 1 2 molar equivalents in the conventional manner: D ₂ -NH ₂ (6) And reacting with a compound of the formula below about 1 molar equivalent: Forming a compound of the formula: And (ii) diazotizing about 1 molar equivalent of the amine of the formula: D ₁ -NH ₂ (9) and having about 1 mole equivalent of the compound of formula (8a) obtained according to (i) The reaction forms a compound of the formula (1) as in the first aspect of the patent application, wherein D ₁ , D ₂ , R ₁ and R ₂ each have the definitions and preferred meanings as given in the first item of the patent application. a compound of the formula: Wherein Y is a vinyl or -CH ₂ -CH ₂ -U group, and U is a group which can be removed under basic conditions, k is the number 2, and m is the number 3. A reactive dye according to any one of claims 1 to 5, or a reactive dye prepared according to claim 6 of the patent application, which is used for a hydroxyl-containing fiber material or a nitrogen-containing fiber material Dye or print. The use of item 8 of the patent application, wherein the cellulose fiber material, in particular the fiber material containing cotton, is dyed or printed. An aqueous ink comprising the reactive dye of the formula (1) of claim 1 of the patent application. A method of printing a textile fiber material, paper or plastic film according to an ink jet printing method, comprising using an aqueous ink as in claim 10 of the patent application.