CN100335561C

CN100335561C - Mixtures of reactive dyes and their use

Info

Publication number: CN100335561C
Application number: CNB200480009038XA
Authority: CN
Inventors: A·茨卡斯; G·勒恩特根
Original assignee: Ciba Spezialitaetenchemie Holding AG
Current assignee: Huntsman Textile Effects Switzerland GmbH
Priority date: 2003-04-01
Filing date: 2004-03-24
Publication date: 2007-09-05
Anticipated expiration: 2024-03-24
Also published as: CN101092523B; CN1768118A; CN101092523A

Abstract

Dye mixtures comprising at least one dye of formula together with at least one dye of formula wherein the radicals indicated in the formulae are defined in accordance with the claims, are suitable for dyeing or printing cellulosic fibre materials with good build-up behaviour and yield dyeings of a deep shade having good fastness properties.

Description

Reactive dye mixture with and use

The present invention relates to be applicable to the filamentary material that comprises nitrogen or comprise hydroxyl is dyeed or prints and produce the dyeing with good all round fastness performance or the reactive dye mixture of printed matter.

The dyeing industry is more and more higher to the requirement of dyeing quality and dyeing course earning capacity recently.Gu this constantly need have good performance, especially has the new dye composition that is easy to obtain of superperformance in its application facet.

At present dyeing need have for example sufficient substantive dyeing power and be easy to wash off the reactive dyestuffs of loose colour simultaneously.It also should show good tinctorial yield and hyperergy, and its purpose is especially in order to obtain to have the dyeing of high colour-fast rate.In many cases, the pile-on properties of reactive dyestuffs can not fully satisfy the requirement that is occurred, and is especially all the more so when dying very dark pool.

Therefore, the problem to be solved in the present invention provides and is specially adapted to filamentary material is dyeed and prints and height indicator reveals the new reactive dye mixture of above-mentioned character.This dyestuff also should be produced has for example dyeing of light fastness and wet fastness of good all round fastness performance.

Therefore, the present invention relates to comprise the dye mixture of the dyestuff of the dyestuff of at least a formula (1) and at least a formula (2),

R wherein ₁And R ₂Be the unsubstituted or substituted C of hydrogen separately independently of one another ₁-C ₈Alkyl,

(R ₃) _0-3(R ₄) _0-3Represent independently of one another that separately 0 to 3 is selected from halogen, C ₁-C ₄Alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group, carboxyl and sulfo group,

D ₁And D ₂Be the radical of a diazo component of benzene or naphthalene series separately independently of one another,

R and s be independently of one another separately the numeral 0 or 1, and r+s and be the numeral 1 or 2,

Y ₁And Y ₂Be other fibre-reactive group of following formula separately independently of one another

-SO ₂-Z (3a)，

-NH-CO-(CH ₂) _m-SO ₂-Z (3b)，

-CONH-(CH ₂) _n-SO ₂-Z (3c)，

-NH-CO-CH(Hal)-CH ₂-Hal (3d)，

-NH-CO-C (Hal)=CH ₂(3e) or

Wherein

X is a halogen, and T has the fibre-reactive group of definition identical with the definition of X or following formula or the substituting group of non--fibre-reactive independently:

-NH-(CH ₂) _2-3-SO ₂-Z (4a)，

-NH-(CH ₂) _2-3-O-(CH ₂) _2-3-SO ₂-Z (4b)，

(R ₅) _0-2Represent 0 to 2 and be selected from halogen, C ₁-C ₄Alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group and sulfo group,

Z is vinyl or group-CH ₂-CH ₂-U and U are a kind of groups that can remove under alkaline condition,

Q is group-CH (Hal)-CH ₂-Hal or-C (Hal)=CH ₂,

M and n be independently of one another separately the numeral 2,3 or 4 and

Hal is a halogen,

While group Y ₁And Y ₂In at least one be the group of formula (3f), and the dyestuff of formula (2) is not the dyestuff of following formula

Wherein

X ^*Be that fluorine and this β-sulfato ethylsulfonyl are bonded on the 4-position, perhaps

X ^*Be that chlorine and this β-sulfato ethylsulfonyl are bonded on the 3-position.

In the group of formula (4c), Me is that methyl and Et are ethyls.With regard to the substituting group on the nitrogen-atoms, outside the dehydrogenation, also consider above-mentioned group.

With regard to R ₁And R ₂The C that is considered ₁-C ₈Alkyl, be independently of one another separately for example methyl, ethyl, propyl group, sec.-propyl, butyl, the second month in a season-butyl, tert-butyl, isobutyl-, just-amyl group, just-hexyl, just-heptyl or just-octyl group.Interested is C ₁-C ₄Alkyl.Abovementioned alkyl can be unsubstituted or substituted, for example, and can be by hydroxyl, sulfo group, sulfato, cyano group, carboxyl, C ₁-C ₄Alkoxyl group or phenyl replace, preferably by hydroxyl, sulfato, C ₁-C ₄Alkoxyl group or replaced by phenyl.Preferably correspondingly unsubstituted group.

With regard to R ₃, R ₄And R ₅The C that is considered ₁-C ₄Alkyl, be independently of one another separately for example methyl, ethyl, just-propyl group, sec.-propyl, just-butyl, the second month in a season-butyl, tert-butyl or isobutyl-, preferably methyl or ethyl and especially methyl.

With regard to R ₃, R ₄And R ₅The C that is considered ₁-C ₄Alkoxyl group, be independently of one another separately for example methoxyl group, oxyethyl group, just-propoxy-, isopropoxy, just-butoxy or isobutoxy, preferably methoxy or ethoxy and especially methoxyl group.

With regard to R ₃, R ₄And R ₅The halogen of being considered is for example fluorine, chlorine or bromine separately independently of one another, preferably chlorine or bromine and especially chlorine.

Preferred R ₁And R ₂One in the base is hydrogen, and another is above-mentioned unsubstituted or substituted C ₁-C ₈One of alkyl.

R ₁And R ₂Especially hydrogen.

(R ₃) _0-3(R ₄) _0-3Preferably represent 0 to 3 separately independently of one another and be selected from C ₁-C ₄Alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group and sulfo group.In an interested embodiment, R ₃And R ₄Each is sulfo group naturally.

(R ₅) _0-2Represent that preferably 0 to 2 is selected from C ₁-C ₄Alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group and sulfo group, especially methyl, methoxyl group and sulfo group.

R ₅Especially hydrogen.

Group D in the dye mixture of the present invention ₁And D ₂The conventional substituting group that can comprise azoic dyestuff.

The replacement base example that can mention comprises: have 1 to 12 carbon atom, the alkyl of 1 to 4 carbon atom especially, as methyl, ethyl, just-or different-propyl group or just-, different-, secondary-or tert-butyl; Have 1 to 8 carbon atom, the alkoxyl group of 1 to 4 carbon atom especially, as methoxyl group, oxyethyl group, just-or different-propoxy-or just-, different-, secondary-or uncle-butoxy; Substituted at moieties, for example by hydroxyl, C ₁-C ₄The C that alkoxyl group or sulfato replace ₁-C ₄Alkoxyl group, for example 2-hydroxyl-oxethyl, 3-hydroxyl propoxy-, 2-sulfato oxyethyl group, 2-methoxy ethoxy or 2-ethoxy ethoxy; Alkanoyl amino, especially C with 2 to 8 carbon atoms ₂-C ₄Alkanoyl is amino as acetylamino or propionyl amino, benzoyl-amido or C ₂-C ₄Alkoxycarbonyl amino such as methoxycarbonyl amino or ethoxy carbonyl-amino, amino, N-be single-or N, N-two-C ₁-C ₄Alkylamino, it can not be substituted or be substituted on moieties separately, for example by hydroxyl, sulfo group, sulfato or by C ₁-C ₄Alkoxyl group replaces, for example methylamino, ethylamino, N, and the N-dimethyl-or N, N-diethylamino, sulfo group methylamino, beta-hydroxy ethylamino, N, N-two (beta-hydroxy ethylamino), N-β-sulfato ethylamino; The phenyl amino that is not substituted or is replaced by methyl, methoxyl group, halogen or sulfo group at phenyl moiety; The N-C that is not substituted or replaces by hydroxyl, sulfo group or by sulfato or replaced by methyl, methoxyl group, halogen or sulfo group at phenyl moiety at moieties ₁-C ₄Alkyl-N-phenyl amino, for example N-methyl-N-phenyl amino, N-ethyl-N-phenyl amino, N-beta-hydroxy ethyl-N-phenyl amino or N-β-sulfo group ethyl-N-phenyl amino; Unsubstituted or by the naphthyl amino of sulfo group-replacement; Have 2 to 8 carbon atoms, especially the alkanoyl of 2 to 4 carbon atoms, for example ethanoyl or propionyl, benzoyl; Partly has the alkoxy carbonyl of 1 to 4 carbon atom at alkoxyl group, as methoxycarbonyl or ethoxy carbonyl; Alkyl sulphonyl with 1 to 4 carbon atom is as methyl sulphonyl or ethylsulfonyl, phenyl-or naphthyl-alkylsulfonyl; Trifluoromethyl; Nitro; Cyano group; Hydroxyl; Halogen is as fluorine, chlorine or bromine; Formamyl; N-C ₁-C ₄Alkyl-carbamoyl is as N-methylamino formyl radical or N-ethylamino formyl radical; Sulfamyl; N-C ₁-C ₄Alkylsulfamoyl group such as N-methyl sulfamyl, N-ethyl sulfamyl, N-propyl group sulfamyl, N-sec.-propyl sulfamyl or N-butyl-sulfamyl, N-(beta-hydroxy ethyl) sulfamyl, N, N-two (beta-hydroxy ethyl) sulfamyl, N-phenyl sulfamoyl base, urea groups, carboxyl, sulfo group methyl, sulfo group or sulfato and also have the fibre-reactive group.This alkyl can also be mingled with aerobic (O-) or amino (NH-,-N (C ₁-C ₄-alkyl)-).

In interested embodiment of the present invention, D ₁And D ₂At least one has at least one fibre-reactive group in the base.

In another interested embodiment of the present invention, D ₁And D ₂Base respectively carries at least one fibre-reactive group.

Thereby the fibre-reactive group should be understood that be can with cellulosic hydroxyl, with wool and silk in amino, carboxyl, hydroxyl and thiol group or the amino and possible carboxyl in the synthesizing polyamides react those groups that form covalent chemical bond.This fibre-reactive group directly is attached on this dye-based or by the bridge member usually and is connected on this dye-based.Suitable fibre-reactive group has and for example has at least one removable substituent those group or wherein said group comprise and be suitable for the group that reacts with filamentary material on aliphatic series, aromatics or heterocyclic radical, vinyl for example, those groups.

Such fibre-reactive group itself is known and many such groups has been described, for example at Venkataraman " chemistry of synthetic dye (The Chemistry ofSynthetic Dyes) ", the 6th volume, the 1-209 page or leaf, Academic Press, New York, London 1972 or in US-A-5 684 138, it is described.

D ₁And D ₂Preferably be the group of formula (5) separately independently of one another,

Wherein

(R ₆) _0-3Represent 0 to 3 and be selected from halogen, C ₁-C ₄-alkyl, C ₁-C ₄Alkoxyl group, carboxyl, nitro and sulfo group, especially halogen, C ₁-C ₄Alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group and sulfo group and

Y ₃Be above-mentioned formula (3a), (3b), (3c), (3d), (3e) or group (3f).

X in the fibre-reactive group of formula (3f) is for example fluorine, chlorine or bromine, preferably fluorine or chlorine and especially chlorine.

T is the substituting group of formula (4a), (4b), (4c), (4d) or fibre-reactive group (4e) or non--fibre-reactive preferably, and especially formula (4a), (4b), (4c), (4d) or fibre-reactive group (4e).

When the substituting group of T right and wrong-fibre-reactive, this substituting group can be a hydroxyl for example; C ₁-C ₄Alkoxyl group; Unsubstituted or substituted, for example by hydroxyl, carboxyl or the C that replaced by sulfo group ₁-C ₄Alkylthio; Amino; By C ₁-C ₈The amino of alkyl list-or two-replace, for this alkyl, it can be unsubstituted or further be replaced, for example by sulfo group, sulfato, hydroxyl, carboxyl or by phenyl, especially replaced by sulfo group or hydroxyl, and be mingled with one or more-O-base; Cyclohexyl amino; The morpholine subbase; N-C ₁-C ₄Alkyl-N-phenyl amino or phenyl amino or naphthyl amino, this phenyl or naphthyl can be unsubstituted or substituted, for example, and by C ₁-C ₄Alkyl, C ₁-C ₄Alkoxyl group, carboxyl, sulfo group or replaced by halogen.

The example of the substituting group T of suitable non--fibre-reactive has amino, methylamino, ethylamino, the beta-hydroxy ethylamino, N-methyl-N-beta-hydroxy ethylamino, N-ethyl-N-beta-hydroxy ethylamino, N, N-two-beta-hydroxy ethylamino, β-sulfo group ethylamino, cyclohexyl amino, the morpholine subbase, 2-, 3-or 4-chloro-phenyl-amino, 2-, 3-or 4-aminomethyl phenyl amino, 2-, 3-or 4-p-methoxy-phenyl amino, 2-, 3-or 4-sulfo group phenyl amino, disulfophenyl amino, 2-, 3-or 4-carboxyl phenyl amino, 1-or 2-naphthyl-amino, 1-sulfo group-2-naphthyl amino, 4,8-disulfo-2-naphthyl amino, N-ethyl-N-phenyl amino, N-methyl-N-phenyl amino, methoxyl group, oxyethyl group, just-or different-propoxy-and hydroxyl.

With regard to the substituting group of non--fibre-reactive, T is C preferably ₁-C ₄Alkoxyl group, be not substituted or by hydroxyl, carboxyl or the C that replaced by sulfo group ₁-C ₄Alkylthio, hydroxyl, amino, separately be not substituted or the N-that replaces by hydroxyl, sulfato or by sulfo group at moieties single-or N, N-two-C ₁-C ₄-alkylamino, morpholine subbase, be not substituted or the phenyl amino that on phenyl ring, replaces or be not substituted or substituted in the same manner N-C by sulfo group, carboxyl, acetylamino, chlorine, methyl or by methoxyl group ₁-C ₄Alkyl-N-phenyl amino (its alkyl be not substituted or replace) or the naphthyl amino that is not substituted or is replaced by 1 to 3 sulfo group by hydroxyl, sulfo group or by sulfato.

Especially preferred non--the substituting group T of fibre-reactive is amino, N-methylamino, N-ethylamino, N-beta-hydroxy ethylamino, N-methyl-N-beta-hydroxy ethylamino, N-ethyl-N-beta-hydroxy ethylamino, N, N-two-beta-hydroxy ethylamino, β-sulfo group ethylamino, morpholine subbase, 2-, 3-or 4-carboxyl phenyl amino, 2-, 3-or 4-sulfo group phenyl amino and N-C ₁-C ₄Alkyl-N-phenyl amino.

In the situation of formula (4a) and fibre-reactive group T (4b), Z is β-chloroethyl preferably.In the situation of formula (4c) and fibre-reactive group T (4d), Z is vinyl or β-sulfato ethyl preferably.

When T was the fibre-reactive group, T is the group of formula (4c) or group (4d), especially formula (4c) preferably.

Hal in formula (3d), (3e) and the fibre-reactive group (4e) is chlorine or bromine, especially bromine preferably.

With regard to leavings group U, for example consider-Cl ,-Br ,-F ,-OSO ₃H ,-SSO ₃H ,-OCO-CH ₃,-OPO ₃H ₂,-OCO-C ₆H ₅,-OSO ₂-C ₁-C ₄Alkyl or-OSO ₂-N (C ₁-C ₄Alkyl) ₂U preferably formula-Cl ,-OSO ₃H ,-SSO ₃H ,-OCO-CH ₃,-OCO-C ₆H ₅Or-OPO ₃H ₂Group, especially-Cl or-OSO ₃H and preferably-OSO ₃H.

Therefore, the example of suitable group Z is that vinyl, β-bromo-or β-chloro-ethyl, β-acetoxyl group ethyl, β-benzoyloxy ethyl, β-phosphate radical close ethyl (phosphatoethoyl), β-sulfato ethyl and β-thiosulfate anion and close ethyl.Z is vinyl, β-chloroethyl or β-sulfato ethyl preferably.

D ₁And D ₂Preferably be the group of following formula separately independently of one another

Especially formula (5a), (5b) or group (5e), wherein

(R _6a) _0-2Represent 0 to 2 and be selected from halogen, C ₁-C ₄Alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group and sulfo group, especially methyl, methoxyl group and sulfo group,

Y _3aBe alpha, beta-2-dibrom propionyl amino or α-bromopropylene acyl amino,

M is a numeral 2 or 3, especially 3,

N be the numeral 2 or 3, especially 2 and

Z ₁, Z ₂, Z ₃And Z ₄Be vinyl, β-chloroethyl or β-sulfato ethyl separately independently of one another.

Z ₁And Z ₂Preferably be vinyl or β-sulfato ethyl separately independently of one another.

Z ₃β-chloroethyl or β-sulfato ethyl, especially β-chloroethyl preferably.

Z ₄β-chloroethyl or β-sulfato ethyl, especially β-sulfato ethyl preferably.

R and s separately preferably the numeral 1 and r+s and be the numeral 2.

Preferred formula (1) dyestuff, wherein

R ₁And R ₂Be hydrogen and

D ₁And D ₂Be that formula (5a), (5b), (5c), (5d) or base (5e) are solid separately independently of one another, preferably formula (5a), (5b) or group (5e), and the group of formula (5a) especially

Group D in the dyestuff of formula (1) ₁And D ₂Identical or different, and preferably different.

Special preferred formula (1) dyestuff, wherein

R ₁And R ₂Be hydrogen,

D ₁It is the group of formula (5aa)

D ₂It is the group of formula (5ab)

Wherein

R _6aAnd R _6bBe methyl or methoxy separately independently of one another, R _6aEspecially methyl and R _6bEspecially methoxyl group and

Z _1aAnd Z _1bBe vinyl, β-chloroethyl or β-sulfato ethyl separately independently of one another

The dyestuff of formula (1) can also be at least a dye mixture at least a and formula (1c) and the compound (1d) that comprises in formula (1a) and the compound (1b);

D wherein ₁And D ₂Be different and

R ₁, R ₂, D ₁And D ₂Have top given definition and preferred implication.

Preferred formula (2) dyestuff, wherein

(R ₃) _0-3(R ₄) _0-3Have top given definition and preferred implication,

R and s each naturally the numeral 1 and r+s and be the numeral 2 and

Fibre-reactive group Y ₁And Y ₂In one be formula (3a), (3b), (3c), (3d) or group (3e) and fibre-reactive group Y ₁And Y ₂In another be the group of formula (3f), Y ₁Especially the group and the Y of formula (3f) ₂Especially formula (3a), (3b), (3c), (3d) or group (3e), the group of formula (3a) more particularly, wherein above given definition and preferred meaning also be applicable to formula (3a), (3b), (3c), (3d), (3e) and fibre-reactive group (3f).In an interested embodiment, R ₃And R ₄Each is sulfo group naturally.

The dyestuff of a kind of especially preferred formula (2) is the dyestuff of formula (2a),

Wherein

(R ₃) _0-2(R ₄) _0-2Represent independently of one another that separately 0 to 2 is selected from C ₁-C ₄Alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group and sulfo group, especially methyl, methoxyl group and sulfo group and

Fibre-reactive group Y ₁And Y ₂In one be formula (3a), (3b), (3c), (3d) or group (3e) and fibre-reactive group Y ₁And Y ₂In another be the group of formula (3f), Y ₁Especially the group and the Y of formula (3f) ₂Especially formula (3a), (3b), (3c), (3d) or group (3e), the group of formula (3a) more particularly, definition that provides above and preferred meaning also are applicable to formula (3a), (3b), (3c), (3d), (3e) and fibre-reactive group (3f).

A kind of more specifically dyestuff of preferred formula (2) is the dyestuff of formula (2aa),

Wherein

X is a halogen, especially chlorine and

Z ₅And Z ₆Have top given definition that is used for Z and preferred implication separately independently of one another, and especially vinyl or β-sulfato ethyl.

Dye mixture of the present invention can be prepared by for example each dyestuff being mixed.This mixing process for example is at suitable shredder, and for example ball mill or sell carries out in the excellent pulverizer, and can carry out in kneader or mixing tank.

The dyestuff of some formulas (1) and (2) is known or can be prepared with known method itself.Among the WO-A-00/06652 dyestuff of formula (1) and the mixture of formula (1a), (1b), (1c) and dyestuff (1d) are being disclosed for example.Dyestuff to formula (2) in US-A-4 662 390 for example is described.

The invention still further relates to the new dye of above-mentioned formula (2aa), each definition and the preferred meaning that wherein provide above also are applicable to X, Z ₅And Z ₆

The dyestuff of formula of the present invention (2aa) is to be prepared by for example with suitable order the compound of each following formula of about 1 molar equivalent being reacted each other,

Wherein X, Z ₅And Z ₆Have top given each definition and preferred meaning.

Suitable cyanuric halogen as formula (9) cyanuryl chloride or cyanuric fluoride, especially cyanuryl chloride arranged.

Admittedly for the step of aforesaid method can be carried out with different order, if desired, carry out simultaneously, can use the diverse ways mutation.This reaction is generally progressively carried out, and carries out the wherein simple reaction between each reactive component according to particular case selective reaction order with favourable.In a preferred embodiment:

(i) with the compound diazotization of an about molar equivalent formula (6) and with its compound coupling mutually with an about molar equivalent formula (7);

(ii) with the compound of an about molar equivalent formula (8) and the compound condensation of an about molar equivalent formula (9);

(iii) a compound and the about molar equivalent with an about molar equivalent formula (10) reacts according to the compound that is (ii) obtained, thereby forms second kind of condensation product; With

(iv) with an about molar equivalent according to this second kind of condensation product diazotization that is (iii) obtained and with itself and the compound coupling mutually that is obtained according to (i).

Said diazotization and coupling are carried out in a usual manner, for example comprise: for example use nitrite such as Sodium Nitrite at low temperatures for example 0 to 5 ℃ of following diazotization in the hydrochloric acid soln at inorganic acid solution with the compound of formula (6) with according to second kind that is (iii) the obtained produce product that contract, then with its with suitable coupling component neutrality to micro acid medium for example pH be 3 to 7, preferred 3 to 4 or 5.5 to 6.5 medium neutralization is at low temperatures as carry out coupling under 0 to 30 ℃.

Condensation reaction is normally used with the currently known methods similar methods and is carried out, generally be in the aqueous solution under 0 to 50 ℃ temperature for example and for example carrying out under 3 to 10 the pH.

The compound of formula (6), (7), (8), (9) and (10) is known or can similarly be prepared with the preparation of known compound.

The reactive dyestuffs of dye mixture Chinese style of the present invention (1) and (2) comprise with the free sulfonic form or preferably with the form of the salt sulfo group that exists of sodium, lithium, potassium or ammonium salt or organic amine salt such as triethanol ammonium salt form for example.

The reactive dyestuffs of formula (1) and (2) can comprise other additive such as sodium-chlor or dextrin, and therefore make this dye mixture also can comprise this other additive.

The exist weight ratio of the dyestuff of formula (1) and (2) in dye mixture of the present invention is for example 1: 99 to 99: 1, is preferably 5: 95 to 95: 5 and especially is 10: 90 to 90: 10.

In suitable situation, the reactive dyestuffs of dye mixture of the present invention and formula of the present invention (2aa) can comprise other auxiliary agent, for example can improve the auxiliary agent of property handled or increase stability in storage, for example buffer reagent, dispersion agent or dedusting agent.This analog assistant is known in those skilled in the art.

The dyestuff of dye mixture of the present invention and formula of the present invention (2aa) is suitable for many widely materials are very dyeed and print and dye, and said material is as comprising hydroxyl or comprising the filamentary material of nitrogen.Example has silk, leather, wool, tynex and urethane and especially all types of cellulosic fibre material.Such cellulosic fibre material for example has, and native cellulose fibre as cotton, flax and hemp, and also has Mierocrystalline cellulose and regenerated Mierocrystalline cellulose.Dye mixture of the present invention and dyestuff of the present invention also are suitable for the fiber that comprises hydroxyl that is present in for example cotton mixture with trevira or tynex of BLENDED FABRIC is dyeed and prints and dyes.Dye mixture of the present invention and dyestuff of the present invention are particularly suited for cellulosic fibre material, and especially those cellulosic fibre materials that comprise cotton dye and print and dye.It also can be used for natural or synthetic polyamide fiber material are dyeed or print and dye.

Therefore, the dyestuff that the invention still further relates to dye mixture of the present invention and formula of the present invention (2aa) is to comprising hydroxyl or comprising filamentary material, the especially Mierocrystalline cellulose of nitrogen, the application in dyeing or printing and dyeing.

The dyestuff of dye mixture of the present invention and formula of the present invention (2aa) can be applied on the filamentary material and can be fixed in every way on the fiber, especially with the form of aqueous dye solutions and print paste.The dyeing that it not only can be used for the process of dying to the greatest extent (exhaust process) but also can be used for carrying out according to pad dyeing, in view of the above, it is that article are flooded with aqueous dye solutions (can comprise salt in suitable situation), handling the back with alkali or having that dyestuff is fixed under the situation of alkali, and in suitable situation, can carry out with logical superheated effect or by it is at room temperature stored several hours.After fixing, with cold water and hot water this dyeing or print are thoroughly cleaned, if necessary, can add the dispersion agent effect and the material loose dye diffusion of promotion.

Dye mixture of the present invention and dyestuff of the present invention are with hyperergy, good fixation ability and very good dye dark ability and be celebrated.Therefore, it is used in using up the process of dying and only need short steaming time in the pad steam dyeing method of carrying out under the low dyeing temperature.Fixation degree height and loose dyestuff can be easily by flush awaies, and the difference between degree of exhaustion and the degree of fixation is very little, and the promptly said loss of soaping is very little.Dye mixture of the present invention and dyestuff of the present invention also are particularly useful for printing and dyeing, especially printing and dyeing of carrying out on cotton, and being applicable to comprising the fiber of nitrogen, for example wool or silk or comprise wool or the BLENDED FABRIC of silk is printed and dyed.

Dyeing of producing with dye mixture of the present invention and dyestuff of the present invention and printing product are acid and all have high tinctorial strength and high fiber-dyestuff combination stability and good light fastness and a very good wet fastness properties in alkaline range, as washable, water-fastly soak, sea water resistance, anti-cross dyeing and fastness to perspiration, and have good anti-folded fastness, fastness to hot pressing and fastness to rubbing.The dyeing of gained shows fiber water levelling (fibre-levelness) and surface water levelling (surface-levelness).

The also suitable tinting material of the dyestuff of dye mixture of the present invention and formula of the present invention (2aa) as register system.Such register system has for example can be by the ink-jet printer that is used for paper or textile printing or writing implement such as fountain pen and ballpoint pen and the especially ink-jet printer of commercial sources acquisition.For this reason, at first make dye mixture of the present invention or dyestuff of the present invention become the form that is applicable to register system.Suitable form has and for example comprises dye mixture of the present invention or dyestuff of the present invention ink as tinting material.This ink can be used ordinary method, is prepared by each component is mixed in the water of desired number.

The substrate of considering comprises the above-mentioned filamentary material that comprises hydroxyl or comprise nitrogen, especially cellulosic fibre material.Said substrate is textile fibre materials preferably.

Paper or plastic film also are the substrates that suits.

The example of the paper that can mention comprises can be by the ink jetting paper of commercial sources acquisition, printing paper, satin paper, plastic-coated paper, for example Epson ink jetting paper, Epson printing paper, Epson satin paper, Epson glossy film (glossy film), the extraordinary ink jetting paper of HP, Encad gloss printing paper (photo glosspaper), Ilford printing paper.Plastic film for example has, the plastic film of transparent or cloudy.Suitable plastic film for example has the 3M transparent film.

According to used type, for example fabrics printing and dyeing or paper printing, viscosity or other physical properties that it may must correspondingly for example regulate this ink, especially to influential those character of the avidity of the substrate of being discussed.

Dyestuff used in this ink should preferably have low salts contg, that is, based on the weight of this dyestuff, it should have the total salts contg less than 0.5% weight.Can for example,, carry out desalination with owing to its preparation and/or owing to the thinner that adds subsequently has the dyestuff desalination of high relatively salts contg as ultrafiltration, reverse osmosis or dialysis by the membrane sepn operation.

Based on the gross weight of this ink, this ink preferably has 1 to 35% weight, 1 to 30% weight especially, the dyestuff total content of preferred 1 to 20% weight.With regard to lower limit, preferred 1.5% weight, preferred again 2% weight and the especially limit of 3% weight.

This ink can comprise the mixable organic solvent of water, for example C ₁-C ₄Alcohol, as methyl alcohol, ethanol, just-propyl alcohol, Virahol, just-butanols, the second month in a season-butanols, uncle-butanols and different-butanols; Acid amides, for example dimethyl formamide and N,N-DIMETHYLACETAMIDE; Ketone or ketols, for example acetone and Pyranton; Ethers, for example tetrahydrofuran (THF) and two  alkane; The heterogeneous ring compound that comprises nitrogen, N-N-methyl-2-2-pyrrolidone N-and 1 for example, 3-dimethyl-2-imidazolidone; Polyalkylene glycol, for example polyoxyethylene glycol and polypropylene glycol; C ₂-C ₆-aklylene glycol and sulfo-glycols, for example ethylene glycol, propylene glycol, butyleneglycol, triglycol, thiodiglycol, hexylene glycol and glycol ether; Other polyvalent alcohol, glycerine and 1,2 for example, 6-hexanetriol; C with polyhydroxy-alcohol ₁-C ₄Alkyl oxide, for example 2-methoxyl group-ethanol, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy) ethanol, 2-[2-(2-methoxy ethoxy)-oxyethyl group] ethanol and 2-[2-(2-ethoxy ethoxy) oxyethyl group] ethanol; Preferred N-N-methyl-2-2-pyrrolidone N-, glycol ether, glycerine or especially 1, the 2-propylene glycol, based on the gross weight of this ink, its consumption is generally 2 to 30% weight, especially 5 to 30% weight and preferably 10 to 25% weight.

This ink can also comprise solubilizing agent, for example ε-Ji Neixianan.

This ink can comprise the thickening material in natural or synthetic source, particularly comprises thickening material in order to regulate viscosity.

The example of the thickening material that can mention comprises can be by alginate thickening material, starch ethers or the Chinese scholartree bean powder ether (locust Bean flour ether) of commercial sources acquisition, especially sodiun alginate itself or be mixed with modified-cellulose, for example methylcellulose gum, ethyl cellulose, carboxymethyl cellulose, Natvosol, methyl hydroxyethylcellulose, hydroxypropylcellulose or Vltra tears especially preferably have the sodiun alginate of the carboxymethyl cellulose of 20 to 25% weight.The synthetic thickening agent that can mention for example has, and those also have the thickening material of polyalkylene glycol based on poly-(methyl) vinylformic acid or poly-(methyl) acrylamide, its molecular weight is for example 2000 to 20 000, for example the mixing polyalkylene glycol of polyoxyethylene glycol or polypropylene glycol or ethylene oxide and propylene oxide.

Based on the gross weight of this ink, the content of such thickening material in this ink is 0.01 to 2% weight, especially 0.01 to 1% weight and preferably 0.01 to 0.5% weight.

This ink can also comprise buffer substance, for example borax, borate, phosphoric acid salt, polyphosphate or citrate.The example that can mention comprises borax, Sodium Tetraborate, sodium tetraborate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tripoly phosphate sodium STPP, five sodium polyphosphates and Sodium Citrate.In order for example to set up 4 to 9,5 to 8.5 pH especially, based on the gross weight of this ink, the buffer reagent consumption is 0.1 to 3% weight especially, preferred 0.1 to 1% weight.

With regard to other additive, this ink can also comprise tensio-active agent or wetting agent.

Suitable tensio-active agent comprises can be by the negatively charged ion or the nonionogenic tenside of commercial sources acquisition.With regard to the wetting agent in the ink of the present invention, for example consider with preferably 0.1 to 30% weight, the especially urea of 2 to 30% weight or from the mixture of Sodium.alpha.-hydroxypropionate (advantageously being the form of 50% to 60% aqueous solution) and glycerine and/or propylene glycol.

This ink preferably has 1 to 40mPas, and especially 1 to 20mPas and be preferably 1 to 10mPas viscosity.

This ink also comprises conventional additives, as foam preventer or especially suppress the sanitas of fungi and/or bacterial growth.Based on the gross weight of this ink, the consumption of such additive is generally 0.01 to 1% weight.

The sanitas of considering comprises the material that produces formaldehyde, for example Paraformaldehyde 96 and three  alkane, the formalin of especially about 30 to 40% weight, imidazolium compounds be 2-(4-thiazolyl) benzoglyoxaline, thiazolium compounds for example 1 for example, 2-benzisothiazole-3-ketone or 2-just-octyl group-isothiazoline-3-ketone, iodine compound, nitrile, phenol, halogenated alkylthio compound or pyridine derivate, especially 1,2-benzisothiazole-3-ketone or 2-just-octyl group-isothiazoline-3-ketone.A kind of suitable sanitas be for example 20% weight 1, the solution (Proxel  GXL) of 2-benzisothiazole-3-ketone in dipropylene glycol.

This ink can also comprise other additive, as fluorizated polymkeric substance or telomer, and for example based on the gross weight of this ink, the polyethoxye perfluoro alcohol of 0.01 to 1% weight (Forafac  or Zonyl  product).

In the spraying print process, on each droplet of this ink is in a controlled manner from the nozzles spray to the substrate.For this reason, mainly use successive ink ejecting method and drop-on-demand method.In the successive ink ejecting method, produce continuously droplet and will be for this printing any unwanted droplet be delivered in the collection container and with its recycling; And in the drop-on-demand method, produce droplet as required and print; Promptly only just produce droplet when needing when printing.For example can produce these droplets by piezoelectricity-ink gun or by thermal energy (effervesce sprays (bubble jet)).Preferably printing of being undertaken by piezoelectricity-ink gun and the printing of carrying out according to the continous inkjet method.

Therefore, ink and such ink of the invention still further relates to the dyestuff that comprises dye mixture of the present invention or formula of the present invention (2aa) are being used for various substrates, especially the application in the textile fibre materials ink jet printing method of printing and dyeing, top definition and preferred meaning also are applicable to this dye mixture, ink and substrate.

The present invention will be described with the following examples.Unless stated otherwise, otherwise given temperature to be ℃ to be that unit provides, and umber is that parts by weight and per-cent are % weight.Weight part interrelates with the ratio and the parts by volume of liter with kg.

Embodiment 1: under 60 ℃, 100 parts of cotton fabrics are incorporated in the dye bath of the dyestuff of the dyestuff that comprises 0.6 part of formula (101) in 1000 parts of water, 5.4 parts of formulas (102) and 60 parts of sodium-chlor.

Making its 60 ℃ after following 45 minutes, to wherein adding 20 parts of anhydrous sodium carbonates.The temperature of this dye bath was kept under 60 ℃ 45 minutes again.Then, the fabric that this is colored cleans in a usual manner and is dry.Obtain having the navy blue dyeing of good fastness performance.

Embodiment 2: as embodiment 1, operates, but replaces the dyestuff of 0.6 part of formula (101) and with the dyestuff of dyestuff 5.4 parts of formulas of replacement (102) of 5.4 parts of formulas (104) with the dyestuff of 0.6 part of formula (103),

Obtain having the navy blue dyeing of good fastness performance equally.

Embodiment 3 to 59: as embodiment 1, operates, still replaces the dyestuff of 0.6 part of formula (101) with the dyestuff of 0.6 part of following formula,

D wherein ¹ _XyAnd D ² _XyConsistent with the group shown in the table 1 separately and in table 2 these groups are defined, it has obtained to have the navy blue dyeing of good fastness performance equally.

Table 1:

Embodiment	D ¹ _xy	D ² _xy	Color and luster
Embodiment	D ¹ _xy	D ² _xy	Color and luster	3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19	D ₁₁ D ₁₂ D ₁₃ D ₁₄ D ₁₅ D ₁₆ D ₁₇ D ₁₈ D ₁₉ D ₂₀ D ₂₁ D ₂₂ D ₂₃ D ₂₄ D ₂₅ D ₂₆ D ₁₀	D ₁₁ D ₁₂ D ₁₃ D ₁₄ D ₁₅ D ₁₆ D ₁₇ D ₁₈ D ₁₉ D ₂₀ D ₂₁ D ₂₂ D ₂₃ D ₂₄ D ₂₅ D ₂₆ D ₁₂	Navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53

D ₁₂ D ₁₀ D ₁₃ D ₁₀ D ₂₁ D ₁₀ D ₁₀ D ₁₀ D ₁₀ D ₁₀ D ₁₀ D ₁₀ D ₁₀ D ₁₀ D ₁₀ D ₁₀ D ₁₀ D ₁₃ D ₁₄ D ₂₉ D ₂₉ D ₂₉ D ₂₉ D ₃₃ D ₂₈ D ₂₈ D ₁₀ D ₁₀ D ₁₁ D ₃₁ D ₃₃ D ₃₄ D ₂₁ D ₃₄

D ₁₀ D ₁₃ D ₁₀ D ₂₀ D ₁₃ D ₁₄ D ₁₅ D ₁₆ D ₁₇ D ₁₈ D ₁₉ D ₂₁ D ₂₂ D ₂₃ D ₂₄ D ₂₅ D ₂₆ D ₂₀ D ₁₁ D ₃₂ D ₃₀ D ₁₀ D ₃₁ D ₃₃ D ₂₈ D ₂₇ D ₂₉ D ₃₁ D ₃₁ D ₁₁ D ₁₁ D ₃₄ D ₃₄ D ₂₁

Navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy navy

54 55 56 57 58 59

D ₃₄ D ₁₀ D ₃₁ D ₁₀ D ₁₃ D ₁₉

D ₁₀ D ₃₄ D ₃₁ D ₃₃ D ₃₂ D ₂₁

Navy navy navy navy navy navy

Table 2:

D _xy

Embodiment 60 to 62: as embodiment 1, operates, still replaces the dyestuff of 5.4 parts of formulas (102) with the dyestuff of 5.4 parts of following formulas,

Obtained having the navy blue dyeing of good fastness performance equally.

Preparation embodiment:

(a) 36.1 parts of 4-(β-sulfato ethylsulfonyl) aniline-2-sulfonic acid is suspended in 300 parts of water, makes its dissolving and it is cooled to 0 ℃ with saturated sodium carbonate solution to neutrality; To wherein adding 7 parts of Sodium Nitrites, 50 parts of ice and 30 parts of concentrated hydrochloric acids and with this mixture diazotization 2 hours.Then, consume excessive nitrite with thionamic acid.

(b) adding has transferred to 31.9 parts of 1-amino-8-hydroxyl naphthalene-3 of 4, the solution of 6-disulfonic acid (H acid) in 500 parts of water with hydrochloric acid with pH in according to the diazonium solution of (a).During coupled reaction, its pH is maintained 3 to 3.5 with sodium-acetate.Obtain formula with free acid form

Monoazo-dyes.

(c) neutral solution of 28.1 parts of 4-(β-sulfato ethylsulfonyl) aniline in 100 parts of water is joined by with in solution stirring to the 200 part water and the suspension that mixture obtained of 200 parts of ice of 19.5 parts of cyanuryl chlorides in 80 parts of acetone.Under 0 to 5 ℃ and under 3 to 4 the pH, under condition of stirring, make this condensation reaction proceed 1 hour.By adding sodium bicarbonate pH is maintained under this value.

(d) with 17.6 part 1, the neutral solution of 3-phenylenediamine-4-sulfonic acid in 180 parts of water joins in the suspension that (c) obtained, and this mixture was stirred one day under 25 ℃ and 6.5 to 7.2 pH.Obtain the formula of free acid form

Compound.

(e) then, in according to the solution of (d), add 250 parts of ice and 60 parts of concentrated hydrochloric acids, with this mixture be cooled to 0 ℃ and with 7 parts of Sodium Nitrites with its at room temperature slow diazotization.

(f) with sodium bicarbonate will according to the pH regulator to 5.5 of the diazonium solution of (e) to 6 and with its under 5.8 to 6.2 pH with the monoazo-dyes coupling that obtains according to (b).When reaction finishes, make this reaction product precipitation by adding Repone K, it is leached, with the saturated potassium chloride solution washing and with it 40 ℃ of following vacuum-dryings.Obtain the compound of the formula (102) of free acid form,

Cotton dyeing has been obtained having the navy color and luster of good all round fastness performance.

Dyeing process I

Under 60 ℃, 100 parts of cotton fabrics are placed into 1500 parts comprise in 45g/l sodium oxide and 2 parts the dye bath according to the preparation reactive dyestuffs that embodiment obtained.Make it at 60 ℃ after following 45 minutes, to wherein adding the 20g/l anhydrous sodium carbonate.Under this temperature, continued dyeing 45 minutes in addition.Then the article that dyed are carried out rinsing, it was soaped under boiling 15 minutes, once more it is carried out rinsing and drying with nonionic detergent.

Another kind as described method supplies the alternate method, can dye under 80 ℃ rather than 60 ℃.

Dyeing process II

Be dissolved in 200 parts of water the dyestuff of 0.1 part of preparation embodiment and to wherein adding 0.5 part of sodium sulfate, 0.1 part of levelling agent (based on the condensation reaction of high fatty amine and ethylene oxide) and 0.5 part of sodium-acetate.Then, with acetic acid (80%) its pH is transferred to 5.5.This dye bath was heated 10 minutes down at 50 ℃, then to wherein adding 10 parts of wool fabrics.In about 50 minutes process, this bath is heated to 100 ℃ temperature and dyeing 60 minutes under this temperature.Then, this dye bath is cooled to 90 ℃ and also takes out the article that are colored.This wool fabric is washed with hot water and cold water, carry out drying with its rotary dehydration and to it then.

Printing process I

When stirring rapidly, with the dyestuff of 3 parts of preparation embodiment be spread across 100 parts comprise 50 part of 5% sodiun alginate thickening material, 27.8 parts of water, 20 parts of ureas, between 1 part-the deposit thickening material of nitrobenzene sodium sulfonate and 1.2 parts of sodium bicarbonates in.This printing and dyeing paste with acquisition like this prints cotton fabric, drying, and with the carrying out of gained the fabric of printing and dyeing in saturation steam, steamed 2 minutes down at 102 ℃.Then, this fabric that has carried out printing is carried out rinsing, it can be soaped under boiling if necessary, and then it is carried out rinsing, carry out drying then.

Printing process II

(a) with the liquid that comprises 30g/l yellow soda ash and 50g/l urea the sateen that has carried out mercerising and handle is carried out pad dyeing (the liquid-absorbent rate is 70%) and be dried.

(b) will carry out pretreated this sateen with drop-on-demand ink gun (effervesce injection), with comprising with step (a)

-15% weight prepares the reactive dyestuffs of the formula (102) of embodiment

-15% weight 1, the 2-propylene glycol and

-70% weight water

Ink print and dye.Make this printing product complete drying and it is fixed 8 minutes in saturation steam under 102 ℃, down washing is being boiled in cold rinsing, carries out rinsing once more and is dried.

Claims

1. a dye mixture comprises the dyestuff of at least a formula (1) and the dyestuff of at least a formula (2)

Wherein

R ₁And R ₂Be hydrogen or unsubstituted C separately independently of one another ₁-C ₈Alkyl,

Y ₁And Y ₂Be the fibre-reactive group of following formula separately independently of one another

SO ₂-Z (3a)，

-NH-CO-(CH ₂) _m-SO ₂-Z (3b)，

-CONH-(CH ₂) _n-SO ₂-Z (3c)，

-NH-CO-CH(Hal)-CH ₂-Hal (3d)，

-NH-CO-C (Hal)=CH ₂(3e) or

Wherein

X is a halogen, and T has the definition identical with the definition of X independently, or the substituting group of the fibre-reactive group of following formula or non--fibre-reactive

-NH-(CH ₂) _2-3-SO ₂-Z (4a)，

-NH-(CH ₂) _2-3-O-(CH ₂) _2-3-SO ₂-Z (4b)，

(R ₅) _0-2Represent 0 to 2 and be selected from halogen, C ₁-C ₄-alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group and sulfo group,

Q is group-CH (Hal)-CH ₂-Hal or-C (Hal)=CH ₂,

M and n be independently of one another separately the numeral 2,3 or 4 and

Hal is a halogen,

While group Y ₁And Y ₂In at least one is the group of formula (3f),

D wherein ₁And D ₂Be the group of formula (5) separately independently of one another,

Wherein

(R ₆) _0-3Represent 0 to 3 and be selected from halogen, C ₁-C ₄-alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group, carboxyl, nitro and sulfo group and

Y ₃Be formula (3a), (3b), (3c), (3d), (3e) or group (3f) as defined above,

And the dyestuff of formula (2) is not the dyestuff of following formula,

Wherein

X ^*Be that fluorine and this β-sulfato ethylsulfonyl are connected on the 4-position, or

X ^*Be that chlorine and this β-sulfato ethylsulfonyl are connected on the 3-position.

2. dye mixture as claimed in claim 1, wherein, D ₁And D ₂Be the group of following formula separately independently of one another

Wherein

(R _6a) _0-2Represent 0 to 2 and be selected from halogen, C ₁-C ₄Alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group and sulfo group,

Y _3aBe alpha, beta-2-dibrom propionyl amino or α-bromopropylene acyl amino,

M is a numeral 2 or 3,

N be the numeral 2 or 3 and

3. dye mixture as claimed in claim 1, wherein R ₁And R ₂Be hydrogen.

4. as dye mixture any in the claim 1 to 3, wherein

R ₁And R ₂Be hydrogen,

D ₁It is the group of formula (5aa)

D ₂It is the group of formula (5ab)

Wherein

R _6aAnd R _6bBe independently of one another separately methyl or methoxy and

Z _1aAnd Z _1bBe vinyl, β-chloroethyl or β-sulfato ethyl separately independently of one another.

5. as dye mixture any in the claim 1 to 3, the dyestuff of its Chinese style (2) is the dyestuff of formula (2a),

Wherein

(R ₃) _0-2(R ₄) _0-2Represent independently of one another that separately 0 to 2 is selected from C ₁-C ₄Alkyl, C ₁-C ₄The identical or different substituting group of alkoxyl group and sulfo group and fibre-reactive group Y ₁And Y ₂In one be formula (3a), (3b), (3c), (3d) or group (3e) and fibre-reactive group Y ₁And Y ₂In another be the group of formula (3f), formula (3a), (3b), (3c), (3d), (3e) and fibre-reactive group (3f) such as claim 1 definition.

6. as the application of dye mixture any in the claim 1 to 5 in the filamentary material that comprises hydroxyl or comprise nitrogen is dyeed or prints and dyes.

7. ink that comprises dye mixture as claimed in claim 1.

8. ink as claimed in claim 7 is about to comprising hydroxyl or comprising application in the ink jet printing method that the filamentary material of nitrogen prints.