HK1115407A

HK1115407A - Azo compounds

Info

Publication number: HK1115407A
Application number: HK08105038.5A
Authority: HK
Inventors: Robert Egli; Thomas Grabenstein
Original assignee: Clariant Finance (Bvi) Limited
Priority date: 2004-12-10
Filing date: 2005-12-12
Publication date: 2008-11-28

Description

Azo compounds

The present invention relates to novel disperse dyes, their preparation and their use for dyeing and printing regenerated or synthetic hydrophobic materials and/or blends comprising regenerated or synthetic hydrophobic materials.

The present invention relates to novel dyes of formula (I) and mixtures thereof:

wherein

R¹Is represented by C_1-2-an alkyl group; an allyl group; a propargyl group; a benzyl group or a phenyl group, in which,

R²represents H; -CH₂CH₂O-R¹；CH₂CH₂CN；C_1-4-an alkyl group; c substituted by one or more substituents selected from_2-4-an alkyl group: halogen, -OH, -OC_1-2-alkyl or-OCOC_1-2-an alkyl group; c_3-4-an alkenyl group; preferably C substituted by-Cl or-Br_3-4-an alkenyl group; a propargyl group; c_2-4alkylene-OCO-C_1-2-an alkyl group; c_2-4alkylene-O (CO) O-C_1-2-an alkyl group; c_1-2-alkylene-COO-R⁵；C_1-2-alkylene-COOCH₂COOR⁵Or C_1-2-alkylene-COOCH₂COR⁶Preferably CH₂CH₂CN，

Wherein R is⁵Is represented by C_1-4-an alkyl group; a benzyl group; c_1-2-an alkoxyethyl group; c_3-4-an alkenyl group; a propargyl group; tetrahydrofurfuryl group; phenyl or by-CH₃、-OCH₃、-COOCH₃or-COOC₂H₅A substituted phenyl group, which is substituted,

R⁶represents CH₃Or a phenyl group,

R³represents H or CH₃。

Unless otherwise specified, any alkyl group present is straight or branched. Substituted alkyl is substituted with the following groups: halogen, -OH, -OC_1-2-alkyl or-OCOC_1-2-an alkyl group; c_3-4-an alkenyl group; preferably C substituted by-Cl or-Br_3-4-an alkenyl group; a propargyl group; c_2-4alkylene-OCO-C_1-2-an alkyl group; c_2-4alkylene-O (CO) O-C_1-2-an alkyl group; c_1-2-alkylene-COO-R⁵；C_1-2-alkylene-COOCH₂COOR⁵Or C_1-2-alkylene-COOCH₂COR⁶。

Any substituted alkyl group present may be substituted with one or more substituents which may be the same or different. The halogen atom is preferably chlorine or bromine.

In formula I, preference is given to

R¹Is represented by C_1-2-an alkyl group; an allyl group; a propargyl group;

R²represents H; -CH₂CH₂O-R¹；CH₂CH₂CN；C_1-4-an alkyl group; an allyl group; a propargyl group; c_2-4alkylene-OCO-C_1-2-an alkyl group; c_1-2-alkylene-COO-R⁵(ii) a Or C_1-2-alkylene-COOCH₂COOR⁵Preferably CH₂CH₂CN，

Wherein R is⁵Is represented by C_1-4-an alkyl group; an allyl group; a benzyl group or a propargyl group,

R³represents H or CH₃，

And mixtures thereof.

Particular preference is given to dyes of the formula (I) and mixtures thereof, in which

R¹Is represented by C_1-2-an alkyl group;

R²represents-CH₂CH₂O-CH₃；-CH₂CH₂CN; an allyl group; a propargyl group; c₂H₄OCOC_1-2-an alkyl group; c₂H₄COO-R⁵Or C_1-2-alkylene-COOCH₂COO-R⁵Preferably CH₂CH₂CN，

Wherein R is⁵Is represented by C_1-2-an alkyl group; an allyl group or a benzyl group, or a substituted benzyl group,

R³represents H or CH₃。

Most preferred are dyes of formula (I) and mixtures thereof, wherein

R¹Represents CH₃，

R²represents-CH₂CH₂O-CH₃；-CH₂CH₂CN；C₂H₄O-CO-C_1-2-an alkyl group; c₂H₄COO-C_1-2-alkyl or C₂H₄COOCH₂COO-R⁵Preferably CH₂CH₂CN，

Wherein R is⁵Is represented by C_1-2-an alkyl group or a benzyl group,

R³represents H.

In the most preferred dyes, the substituent R¹Represents CH₃。

In the most preferred dyes, the substituent R³Represents H.

In the most preferred dyes, the substituent R²Represents CH₂CH₂CN。

In still more preferred dyes, the substituent R³Represents CH₃。

The novel compounds of the formula (I) and mixtures thereof are very useful disperse dyes.

By diazotisation of amines of the formula (II)

Coupling with amines of the formula (III) to prepare these dyes,

wherein all substituents have the meaning as defined above.

The diazotization and coupling are carried out by generally known methods. For example diazotisation with sodium nitrite in an acidic aqueous medium. Other diazotisation reagents such as mixed acids (a mixture of concentrated nitric acid and concentrated sulfuric acid) may also be used. During the diazotisation, further acids may be present in the reaction medium, for example phosphoric acid, sulfuric acid, acetic acid, propionic acid, hydrochloric acid or mixtures of these acids, for example mixtures of phosphoric acid and acetic acid. The diazotisation is suitably carried out at a temperature in the range-10 to 10 c, preferably 0-5 c.

The coupling of the diazotized compound of the formula (II) with the coupling component of the formula (III) is carried out in a known manner, for example in an acidic, aqueous or aqueous-organic medium, preferably at a temperature in the range from 0 to 50 ℃ and more preferably from 20 to 40 ℃. The acids used are, for example, hydrochloric acid, acetic acid, sulfuric acid or phosphoric acid. For example, the diazotization and coupling may be carried out in the same reaction medium.

Alkali metal nitrites (e.g. sodium nitrite) in solid form or in aqueous solution or in nitrososulphuric acid are used as nitrosating agents.

Electrophilic ionic aryl-N is typically formed by reaction with excess nitrous acid or the like (e.g., nitrososulfuric acid) at low temperatures₂ ⁺The preparation of diazonium ions is disclosed, for example, in the Advanced Organic Chemistry, Fieser&Fieser, page 736-740 or Organische Chemie, K.Peter C.Vollhardt, page 1154-1157, 1. Australia 1988.

The compounds of the formulae (II) and (III) are known or can be prepared readily by methods familiar to the person skilled in the art.

The novel dyes of the formula (I) and mixtures thereof are useful for dyeing and printing semi-synthetic and preferably synthetic hydrophobic fibre materials, in particular textile materials. Textile materials consisting of blended fabrics comprising such semi-synthetic hydrophobic fibre materials may also be dyed or printed with the dyes of the present invention.

Suitable semisynthetic textile materials are mainly cellulose-21/2 acetate, cellulose triacetate, polyamide and high molecular weight polyesters and polyurethanes and mixtures thereof with cellulose.

The synthetic hydrophobic textile material consists essentially of: linear aromatic polyesters, for example terephthalic acid and glycols (in particular ethylene glycol) or condensates of terephthalic acid with 1, 4-bis (hydroxymethyl) cyclohexane; polycarbonates, such as those composed of α, α -dimethyl-4, 4' -dihydroxydiphenylmethane and phosgene; and fibers based on polyvinyl chloride, polyamide and polyurethane. A preferred hydrophobic textile material for use as a substrate is a mixture of polyurethane and polyester fibers.

The synthetic hydrophobic material may be in the form of a sheet-like or yarn-like structure and may be processed, for example, into a yarn or a woven, knit or terry fabric. The novel dyes are also suitable for dyeing synthetic hydrophobic materials in microfibre form.

The novel dyes of the formula (I) can be converted conveniently before use in dye preparations. The dye is ground to particles having an average particle size of 0.1 to 10 microns. The milling may be carried out in the presence of a dispersant. The wet dye is typically milled using a dispersant, followed by vacuum drying or spray drying. Printing pastes and dye baths may be prepared by adding water to the formulations prepared as above.

The novel dyes of formula (I) are applied to textile materials by known dyeing or printing methods, for example as described in french patent application 1,445,371.

Polyester fibre materials are usually dyed from aqueous dispersions by the exhaust process in the presence of customary anionic or nonionic dispersants, in the presence or absence of customary swelling agents (carriers) at from 65 to 140 ℃.

Cellulose-21/2 acetate is preferably dyed at 65-85 ℃ and cellulose triacetate is preferably dyed up to 115 ℃.

The novel dyes are suitable for dyeing by the thermosol process, the exhaust process, the continuous process and for modern imaging processes, such as thermal transfer printing, inkjet printing, hot-melt inkjet printing or printing by conventional printing processes.

Thermosol, dip and continuous methods are well known dyeing methods, see for example "grundagen der textiledren" described in m.peter and h.k.rouette; handbuchder technology, Verfalhren und Maschinen ", revised 13 th edition, 1989, Deutscher Fachverlag GmbH, Frankfurt am Main, Germany, ISBN 3-87150-; among these are the following page numbers: pages 460, 482, 495, 556, 566, and 574, 587.

In the ink jet printing process, individual droplets of ink are sprayed from a nozzle onto a substrate in a controlled manner. The continuous ink jet process and the drop-on-demand process are mainly used for this purpose. In the case of using the continuous ink jet method, droplets are continuously generated, and droplets not requiring printing are transferred to a collector and circulated. In contrast, in the case of using a discontinuous drop-on-demand method, drops are generated and printed on demand, i.e. only when printing is required. The droplets may be generated, for example, by a piezoelectric ink jet head or by thermal energy (bubble jet).

In hot melt ink jet printers, a solid hot melt ink is loaded into a printer that melts the ink in an ink jet printer head, ejects a liquid ink, and rapidly resolidifies upon impact with a substrate. Conventional hot melt ink jet printers operate using a print head with an ink jet temperature of about 120 to about 150 ℃. At such temperatures, the solid ink is melted to a low viscosity liquid, typically about 8-25cP as measured at the jetting temperature.

Conventional printing processes are known, which differ from one another in the way in which the printing ink or printing paste is transferred to the substrate, for example the ink or printing paste can be applied from flat (offset), from concave (intaglio) or by raised means (for example letterpress, offset) by means of stencil (screen printing). Different application methods and different substrates require inks of different properties.

Dyeing is carried out by the exhaust process from an aqueous liquor, the bath ratio being selected from a wide range, for example from 1: 4 to 1: 100, preferably from 1: 6 to 1: 50.

The dyeing time is 20 to 90 minutes, preferably 30 to 60 minutes. The dye liquors may also contain further additives, such as dyeing auxiliaries, dispersants, wetting agents and defoamers.

The dye liquors may also comprise inorganic acids, for example sulphuric acid or phosphoric acid, or also suitably organic acids, for example formic acid or acetic acid, and/or salts, for example ammonium acetate, ammonium sulphate or sodium sulphate. The acid is mainly used for adjusting the pH of the dye liquor, and the pH is preferably in the range of 4-5.

Disperse dyes are usually present in the dye liquors in the form of fine dispersions. Suitable dispersants for preparing the dispersion are, for example, anionic dispersants, such as aromatic sulfonic acid/formaldehyde condensates, sulfonated cresol oil/formaldehyde condensates, lignosulfonates or copolymers of acrylic acid derivatives, preferably aromatic sulfonic acid/formaldehyde condensates or lignosulfonates; or nonionic dispersants based on polyalkylene oxides, for example obtained by polyaddition of ethylene oxide or propylene oxide. Other suitable dispersants are listed in us patent 4,895,981 or us patent 5,910,624.

Suitable inks or printing pastes comprise a) at least one dye of the formula (I) or a mixture of compounds of the formula (I), b) water or a medium comprising a mixture of water and an organic solvent, an anhydrous organic solvent or a low-melting solid, and c) optionally further additives.

Preferably, the ink or printing pastes comprise the dyes of the above formula (I) in a total amount of from 1 to 35%, in particular from 2 to 35%, preferably from 2 to 30%, more preferably from 2.5 to 20%, based on the total weight of the ink or printing paste.

The ink comprises 99 to 65% by weight, in particular 98 to 65% by weight, preferably 98 to 70% by weight, more preferably 97.5 to 80% by weight, of the abovementioned medium b) which comprises water or a mixture of water and an organic solvent, an anhydrous organic solvent or a low-melting solid.

When the medium b) is a mixture comprising water and an organic solvent or an anhydrous organic solvent, it is preferred that the dye of formula (I) or the mixture thereof is completely dissolved in the medium.

Preferably, the solubility (20 ℃) of the dyes of formula (I) or mixtures thereof in the medium b) is not less than 2.5% by weight.

When the ink composition of the invention is used for printing paper substrates or hydrophobic substrates made of acetate-, polyester-, polyamide-, polyacrylonitrile-, polyvinyl chloride-or polyurethane-polymers and blends thereof, it is preferred to use an ink of the following composition.

When the medium is a mixture of water and an organic solvent, the weight ratio of water to organic solvent is preferably from 99: 1 to 1: 99, more preferably from 99: 1 to 50: 50, particularly preferably from 95: 5 to 80: 20.

The organic solvent contained in the mixture with water is preferably a water-soluble solvent or a mixture of various water-soluble solvents. A preferred water-soluble organic solvent is C_1-6Alcohols, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol and cyclohexanol; linear amides, preferably dimethylformamide or dimethylacetamide; ketones and ketoalcohols, preferably acetone, methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; water-miscible ethers, preferably tetrahydrofuran and dioxane; diols, preferably diols having from 2 to 12 carbon atoms, such as 1, 5-pentanediol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, thiodiglycol and oligo-and polyalkylene glycols, preferably diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol; triols, preferably glycerol and 1, 2, 6-hexanetriol; mono-C of diols_1-4Alkyl ethers, preferably mono-C of glycols having 2 to 12 carbon atoms_1-4Alkyl ethers, particularly preferably 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- [2- (2-methoxyethoxy) ethoxy]Ethanol, 2- [2- (2-ethoxyethoxy) ethoxy]Ethanol and ethylene glycol monoallyl ether; ring (C)Amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, caprolactam and 1, 3-dimethylimidazolidinone; cyclic esters, preferably caprolactone; sulfoxides, preferably dimethyl sulfoxide and sulfolane.

In a preferred composition, medium b) comprises water and at least two or more, more preferably 2 to 8, water-soluble organic solvents.

Particularly preferred water-soluble solvents are cyclic amides, in particular 2-pyrrolidone, N-methylpyrrolidone and N-ethylpyrrolidone; diols, preferably 1, 5-pentanediol, ethylene glycol, thiodiglycol, diethylene glycol and triethylene glycol; and mono-C of diols_1-4Alkyl and di-C_1-4mono-C of alkyl ethers, more preferably of diols having 2 to 12 carbon atoms_1-4Alkyl ethers, particularly preferably 2- [2- (2-methoxyethoxy) ethoxy]And (3) ethanol.

Preferred media b) include:

(i)75 to 95 parts by weight of water, and

(ii)25-5 parts of one or more of the following solvents: diethylene glycol, 2-pyrrolidone, thiodiethylene glycol, N-methylpyrrolidone, cyclohexanol, caprolactone, caprolactam and 1, 5-pentanediol,

wherein parts are parts by weight and all parts of (i) and (ii) add up to 100.

Examples of other useful ink compositions comprising water and one or more organic solvents can be found in US 4963189, US 4703113, US 4626284 and EP 425150A.

When medium b) comprises an anhydrous (i.e. less than 1% by weight of water) organic solvent, the boiling point of the solvent is in the range from 30 to 200 deg.C, more preferably from 40 to 150 deg.C, and particularly preferably from 50 to 125 deg.C.

The organic solvent may be water-insoluble, water-soluble or a mixture of these solvents. Preferred water-soluble organic solvents are all the above-mentioned water-soluble organic solvents and mixtures thereof.

Preferred water-insoluble solvents include, in particular, aliphatic hydrocarbons; esters, preferably ethyl acetate; chlorinated hydrocarbons, preferably CH₂Cl₂(ii) a And ethers, preferably diethyl ether; and mixtures thereof.

When the liquid medium b) comprises a water-insoluble organic solvent, it is preferred to add a polar solvent to increase the solubility of the dye in the liquid medium.

An example of such a polar solvent is C_1-4-an alcohol, preferably ethanol or propanol; the ketone is preferably methyl ethyl ketone.

The anhydrous organic solvent may consist of a single solvent or a mixture of two or more different solvents.

When a mixture of different solvents is used, it is preferred to include a mixture of 2 to 5 different anhydrous solvents. This allows good control of the drying properties and stability of the ink composition during storage of the medium b).

Of particular interest are ink compositions comprising anhydrous organic solvents or mixtures thereof when fast drying times are required, particularly when used for printing on hydrophobic and non-absorbent substrates such as plastics, metals and glass.

The preferred low melting point medium has a melting point of 60-140 ℃. Useful low melting solids include long chains (preferably having C)_18-24-carbon chain) fatty acids or alcohols and sulfonamides. Conventional low melting ink vehicles typically include waxes, resins, plasticizers, tackifiers, viscosity modifiers, and antioxidants in various proportions.

The ink compositions and printing pastes of the invention may also comprise further components as auxiliaries, which are customarily used in ink-jet inks or printing pastes, such as buffers, viscosity improvers, surface tension improvers, anchorage accelerators, antimicrobial agents (biozides), corrosion inhibitors, levelling agents, drying agents, wetting agents, ink penetration additives, light stabilizers, UV absorbers, optical brighteners, setting inhibitors, ionic or nonionic surfactants and conductive salts. These auxiliaries are preferably added to the ink in amounts of from 0 to 5% by weight. In the case of printing pastes, preference is given to adding up to 70%, in particular up to 60%, preferably up to 55%, by weight of auxiliaries, based on the total weight of the printing paste.

In order to prevent precipitation in the ink composition of the present invention, the dye used must be purified. Purification can be carried out by a generally known purification method.

When the composition of the present invention is used for printing textile fibre materials, the following composition is preferably used.

When printing textile fibre materials, useful additives are synthetic thickeners, natural thickeners or modified natural thickeners which may comprise water-soluble nonionic cellulose ethers, alginates or bean gum (bean gum) ethers, in addition to solvents comprising water. All water-soluble nonionic cellulose ethers, alginates and bean gum ethers act as thickeners to adjust the ink to a certain viscosity.

Examples of water-soluble nonionic cellulose ethers which can be used are methyl-, ethyl-, hydroxyethyl-, methylhydroxyethyl-, hydroxypropyl-or hydroxypropylmethyl-cellulose. Preference is given to methylcellulose or, in particular, hydroxyethylcellulose. The amount of cellulose ether generally used in the ink is from 0.01 to 2%, in particular from 0.01 to 1%, preferably from 0.01 to 0.5%, based on the total weight of the ink.

Usable alginates include in particular alkali metal alginates, preferably sodium alginate. The amounts of these alginates usually used in the inks are from 0.01 to 2%, in particular from 0.01 to 1%, preferably from 0.01 to 0.5%, based on the total weight of the ink.

The printing pastes contain up to 70% by weight of thickener, preferably up to 55% by weight. The thickening agent is used in the printing paste in an amount of 3 to 70%, in particular 5 to 60%, preferably 7 to 55%, based on the total weight of the printing paste.

In the inkjet printing process, the viscosity of the ink composition is preferably from 1 to 40mPa.s, in particular from 5 to 40mPa.s, preferably from 10 to 40 mPa.s. Particularly preferred are ink compositions having a viscosity of 10 to 35 mpa.s.

The ink composition preferably has a surface tension of from 15 to 73mN/m, in particular from 20 to 65mN/m, particularly preferably from 30 to 50 mN/m.

The conductivity of the ink composition is preferably from 0.1 to 100mS/cm, in particular from 0.5 to 70mS/cm, particularly preferably from 1.0 to 60 mS/cm.

The inks may also comprise buffer substances, such as acetates, phosphates, borax, borates or citrates. Examples thereof are sodium acetate, disodium hydrogen phosphate, sodium borate, sodium tetraborate and sodium citrate.

The dyeings or prints obtained in this way have good all-round fastness properties; particularly remarkable are excellent heat migration fastness, heat fixing fastness and folding fastness, particularly wet fastness.

In the following examples, parts and percentages are parts by weight and percentages by weight. The temperature is given in degrees centigrade.

Example 1

Diazotization

15.4 parts of 2-amino-5-nitrophenol are dissolved in 13.7 parts of cold 30% sodium hydroxide solution. 36.5 parts of 30% HCl are added, followed by 6.9 parts of an aqueous solution of sodium nitrite (40%) at 0-5 ℃ over 1 hour. The solution was stirred at 0-5 ℃ for 2 hours, followed by the addition of 0.1 part of sulfamic acid to destroy excess sodium nitrite.

Coupling of

A solution of 20.8 parts of N-cyanoethyl-N-methoxyethylaminobenzene in 100 parts of glacial acetic acid is added continuously to the diazonium salt solution. The solution was stirred at 30 ℃ for 24 hours. The precipitated dye was filtered off, washed with water and dried under vacuum at 60 ℃.

Isolated dyes of the formula (IV)

λ of_max505nm (in DMF), the polyester is dyed in a red shade and has good allround fastness properties, in particular good wet fastness properties.

TABLE 1/examples 2 to 15

Ex.No.	R³	R²	R¹	λ_maxDMF[nm]
Ex.No.	R³	R²	R¹	λ_maxDMF[nm]	2	H	-CH₂CH₂CN	-CH₂CH₃	5％
3	H	-CH₂CH₂CN	-CH₂CH≡CH	504	2	H	-CH₂CH₂CN	-CH₂CH₃	5％
3	H	-CH₂CH₂CN	-CH₂CH≡CH	504	4	H	-CH₂CH₂CN	-CH₂CH＝CH₂	504
5	H	-CH₂CH₂CN	-CH₂C₆H₅	501	4	H	-CH₂CH₂CN	-CH₂CH＝CH₂	504
5	H	-CH₂CH₂CN	-CH₂C₆H₅	501	6	H	-CH₂CH₂CN	-C₆H₅	498
7	H	-CH₂CH₅	-CH₃	523	6	H	-CH₂CH₂CN	-C₆H₅	498
7	H	-CH₂CH₅	-CH₃	523	8	H	-CH₂CH＝CH₂	-CH₃	515
9	H	-CH₂CH＝CH-Cl	-CH₃	511	8	H	-CH₂CH＝CH₂	-CH₃	515
9	H	-CH₂CH＝CH-Cl	-CH₃	511	10	H	-CH₂CH≡CH	-CH₃	508
11	H	-CH₂CH(OH)CH₂-Cl	-CH₃	510	10	H	-CH₂CH≡CH	-CH₃	508
11	H	-CH₂CH(OH)CH₂-Cl	-CH₃	510	12	H	-CH₂CH(OCOCH₃)CH₂OCOCH₃	-CH₃	502
13	H	-CH₂CH₂COOCH₃	-CH₃	508	12	H	-CH₂CH(OCOCH₃)CH₂OCOCH₃	-CH₃	502
13	H	-CH₂CH₂COOCH₃	-CH₃	508	14	H	-CH₂CH₂COOC₂H₅	-CH₃	510
15	H	-CH₂CH₂COOCH₂C₆H₅	-CH₃	509	14	H	-CH₂CH₂COOC₂H₅	-CH₃	510

TABLE 2/examples 16 to 30

Ex.No.	R³	R²	R¹	λ_maxDMF[nm]
Ex.No.	R³	R²	R¹	λ_maxDMF[nm]	16	H	-CH₂CH₂COOCH₂CH＝CH₂	-CH₃	508
17	H	-CH₂CH₂COOC₂H₄OCH₃	-CH₃	510	16	H	-CH₂CH₂COOCH₂CH＝CH₂	-CH₃	508
17	H	-CH₂CH₂COOC₂H₄OCH₃	-CH₃	510	18	H	-CH₂CH₂COOC₂H₄OC₂H₄OCH₃	-CH₃	510
19	H	-CH₂CH₂COOCH₂COOCH₃	-CH₃	509	18	H	-CH₂CH₂COOC₂H₄OC₂H₄OCH₃	-CH₃	510
19	H	-CH₂CH₂COOCH₂COOCH₃	-CH₃	509	20	H	-CH₂CH₂COOCH₂COOC₂H₅	-CH₃	511
21	H	-CH₂CH₂COOCH₂COOCH₂C₆H₅	-CH₃	510	20	H	-CH₂CH₂COOCH₂COOC₂H₅	-CH₃	511
21	H	-CH₂CH₂COOCH₂COOCH₂C₆H₅	-CH₃	510	22	H	-CH₂CH₂COOCH₂COO-2-terahydrofurfuryl	-CH₃	512
23	H	-CH₂CH₂COOCH₂COOC₆H₄-4-COOCH₃	-CH₃	508	22	H	-CH₂CH₂COOCH₂COO-2-terahydrofurfuryl	-CH₃	512
23	H	-CH₂CH₂COOCH₂COOC₆H₄-4-COOCH₃	-CH₃	508	24	H	-CH₂CH₂OCOCH₃	-CH₃	507
25	H	-CH₂CH₂OCOOCH₃	-CH₃	505	24	H	-CH₂CH₂OCOCH₃	-CH₃	507
25	H	-CH₂CH₂OCOOCH₃	-CH₃	505	26	H	-CH₂CH₂OCOC₂H₅	-CH₃	509
27	-CH₃	-CH₂CH₂CN	-CH₃	519	26	H	-CH₂CH₂OCOC₂H₅	-CH₃	509
27	-CH₃	-CH₂CH₂CN	-CH₃	519	28	-CH₃	-CH₂CH₂CN	-CH₂CH₃	524
29	-CH₃	-CH₂CH₂CN	-CH₂CH≡CH	522	28	-CH₃	-CH₂CH₂CN	-CH₂CH₃	524
29	-CH₃	-CH₂CH₂CN	-CH₂CH≡CH	522	30	-CH₃	-CH₂CH₂CN	-CH₂CH＝CH₂	522

Application example A

17.5 parts of the dye of example 1 in the form of a wet cake are wet-ground using 32.5 parts of a commercial lignosulfonate-based dispersant and subsequently ground to a powder in a known manner. 1.2 parts of this dye preparation are added to 2000 parts of demineralized water at 70 ℃ containing 40 parts of ammonium sulfate, and the pH of the dyeing bath is adjusted to 5 using 85% formic acid. 100 parts of the washed polyester fiber fabric were placed in the dyeing bath, the container was sealed, heated to 130 ℃ within 20 minutes, and dyeing was continued at this temperature for a further 60 minutes. After cooling, the polyester fiber fabric was removed from the dyeing bath and subsequently rinsed, soaped and reductively cleaned using sodium dithionite using conventional methods. After heat fixing (180 ℃ C., 30 seconds), a bright red dyeing is obtained, the overall fastnesses, in particular the light and sublimation fastnesses, and in particular the wet fastnesses, being very good. The dyes of examples 2 to 30 can be used in a similar manner to give dyeings having very good allround fastnesses.

Polyester yarn can be similarly dyed using the dyes of examples 2-30.

Application example B

2.5 parts of the dye obtained in example 1 are dissolved with stirring in a mixture of 20 parts of diethylene glycol and 77.5 parts of water at 25 ℃ to give a printing ink suitable for ink-jet printing.

The dyes of examples 2 to 30 or the dye mixtures of examples 1 to 30 can also be used in a similar manner to that described in application example B.

Application example C

The printing and dyeing paste consists of the following substances:

500g of thickener (Bean Gum Ether, e.g. Indalca)^TM)，

10g fixation accelerator (e.g., Pritogen HDN)^TM)，

10g of levelling agent (e.g. Sandogen CN)^TM)，

10g of a dye buffer and dispersant system (e.g., Sandacid PB)^TM(ii) a 1: 2); and

10g of the dye of example 1

And water was added to 1000 g.

(Indalca is available from Cesalpinia S.p.A., Italy; Sandogen, Printogen and Sandacid are trademarks of Clariant AG, Muttenz/Switzerland.)

The printing and dyeing paste is used for printing paper substrates, textile fiber materials, plastic films and plastic transparent sheets.

The dyes of examples 2 to 30 or the dye mixtures of examples 1 to 30 can also be used in a similar manner to that described in application example C.

Application example D

Using the printing pastes of application example C, polyester interlock knits were printed using a conventional printing press. The resulting printed fabric was dried at 110 ℃ for 3 minutes and then treated with hot steam at 175 ℃ for 7 minutes. The fabric was rinsed with cold tap water for 5 minutes followed by a rinse with demineralized water for 5 minutes. The fabric thus treated was incorporated at 4g/lNa₂CO₃2g/l sodium dithionite (85%) and 1g/l Lyogen DFT^TM(trade mark of Clariantag AG, Muttenz, Switzerland) in a bath. Rinsed with tap water for a further 15 minutesFollowed by a final drying step. The polyester fabrics obtained are printed in bright red and have very good overall fastnesses, in particular excellent lightfastness and sublimation fastness, in particular excellent wet fastness.

The dyes of examples 2 to 30 or the dye mixtures of examples 1 to 30 can also be used in a similar manner to that described in application example D.

Application example E

The ink jet printing composition is preferably prepared by heating the medium to 40 ℃ followed by the addition of the dye of example 1. The mixture was stirred until the dye dissolved. The composition was then cooled to room temperature and the other components were added.

The ink composition comprises the following components:

6 parts of the dye of example 1,

20 parts of glycerol, and

74 parts of water.

The ink composition is used for printing paper substrates, textile fiber materials and plastic films and transparent plastic sheets.

The dyes of examples 2 to 30 or the dye mixtures of examples 1 to 30 can also be used in a similar manner to that described in application example E.

Application example F

The polyester interlock knit was ink jet printed using the printing ink of application example E. The printed fabric was treated similarly to the post-printing treatment of application example D. The polyester fabrics obtained are printed in bright red and have very good overall fastnesses, in particular excellent lightfastness and sublimation fastness, in particular excellent wet fastness.

The dyes of examples 2 to 30 or the dye mixtures of examples 1 to 30 can also be used in a similar manner to that described in application example F.

Claims

1.A dye of formula (I) and mixtures thereof:

wherein

R²represents H; -CH₂CH₂O-R¹；CH₂CH₂CN；C_1-4-an alkyl group;c substituted by one or more substituents selected from_2-4-an alkyl group: halogen, -OH, -OC_1-2-alkyl or-OCOC_1-2-an alkyl group; c_3-4-an alkenyl group; preferably C substituted by-Cl or-Br_3-4-an alkenyl group; a propargyl group; c_2-4alkylene-OCO-C_1-2-an alkyl group; c_2-4alkylene-O (CO) O-C_1-2-an alkyl group; c_1-2-alkylene-COO-R⁵；C_1-2-alkylene-COOCH₂COOR⁵Or C_1-2-alkylene-COOCH₂COR⁶Preferably CH₂CH₂CN，

R⁶represents CH₃Or a phenyl group,

R³represents H or CH₃。

2. The dye of claim 1 and mixtures thereof, wherein

R¹Is represented by C_1-2-an alkyl group; an allyl group; a propargyl group;

R³represents H or CH₃。

3. The dye of claim 2 and mixtures thereof, wherein

R¹Is represented by C_1-2-an alkyl group;

R³represents H or CH₃。

4. The dye of claim 3 and mixtures thereof, wherein

R¹Represents CH₃，

R²represents-CH₂CH₂O-CH₃；-CH₂CH₂CN；C₂H₄O-CO-C_1-2-an alkyl group; c₂H₄COO-C_1-2-alkyl or C₂H₄COOCH₂COO-R⁵Preferably CH₂CH₂CN, preferably CH₂CH₂CN，

Wherein R is⁵Is represented by C_1-2-an alkyl group or a benzyl group,

R³represents H.

5. A process for preparing a dye of the formula (I) according to any of the preceding claims, characterized in that a diazotized amine of the formula (II)

Wherein all substituents have the meanings given in any of the preceding claims, with amines of the formula (III)

Wherein all substituents have the meaning given in any one of the preceding claims.

6. Use of a disperse dye of formula (I) or a mixture thereof according to any one of claims 1 to 4 in dyeing or printing fibres or yarns or materials prepared therefrom, including fully synthetic or semi-synthetic hydrophobic organic materials, preferably a mixture of polyester and polyurethane.

7. Use of a disperse dye of the formula (I) or a mixture thereof according to any of claims 1 to 4 in an ink-jet printing process or a hot-melt ink-jet process.

8. A composition comprising a dye of formula (I) according to any one of claims 1 to 4 or a mixture thereof.

9. The composition of claim 8, wherein the composition is a printing paste or printing ink or ink jet printing ink or hot melt ink jet printing ink.

10. A fibre or yarn dyed or printed with a dye of formula (I) or a mixture thereof according to any one of claims 1 to 4 or a material prepared therefrom, said material comprising fully synthetic or semi-synthetic hydrophobic organic material.