HK1084144B - Azo compounds - Google Patents

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 mixtures containing regenerated or synthetic hydrophobic materials.

The invention relates to novel dyes of formula (I)

Wherein

X represents H; halogen, preferably Cl or Br; -CN; -SO₂CH₃；-OH；-OCH₃or-NO₂，

Y represents H; halogen, preferably Cl or Br; or-CN, and

k represents 6-hydroxypyridone-2, aniline, alpha-naphthylamine, 5-aminopyrazole, 5-hydroxypyrazole, indole, tetrahydroquinoline, 2-aminothiazole, 2-aminothiophene, phenole which is not substituted by 3, 5-dimethyl and in which the substituents in the 3-and 5-positions are not a ring member of the second, 2-naphthol, benzomorpholine or a coupling component group of the 2, 6-diaminopyridine series.

In formula I, preference is given to

X represents H; halogen, preferably Cl or Br; -CN or-NO₂，

Y represents H; halogen, preferably Cl or Br; or-CN, and

k represents a coupling component radical of the series 6-hydroxypyridone-2, aniline, alpha-naphthylamine, 5-aminopyrazole, 5-hydroxypyrazole, indole, tetrahydroquinoline, 2-aminothiazole, 2-aminothiophene, 2-naphthol, benzomorpholine or 2, 6-diaminopyridine.

More preferred coupling component groups K are of the 5-hydroxypyrazole, 6-hydroxypyridone-2 or aniline series.

More preferred coupling component groups K are the 6-hydroxypyridone-2 or aniline series.

The most preferred coupling component group K is the 5-hydroxypyrazole series.

Particular preference is given to dyes of the formula (I-A)

Wherein

X represents H; halogen, preferably Cl or Br; -CN, -OH; -OCH₃or-NO₂，

Y represents H; halogen, preferably Cl or Br; or-CN, and

R¹is represented by C_1-6-an alkyl group; substituted C_2-4-alkyl, preferably substituted by one or more groups selected from halogen, -CN, -SCN, -OC_1-4-alkyl, -OCOC_1-3-alkyl, -OCHO, -OC₆H₅and-C₆H₅Substituent substitution of the composition；C_3-4-an alkenyl group; substituted C_3-4-alkenyl, preferably substituted by-Cl or-Br; c_3-4-alkynyl, preferably propargyl; c_2-4alkylene-OCO-C_1-3-an alkyl group; c_2-4alkylene-O (CO) O-C_1-3-an alkyl group; c_1-3alkylene-COO-R⁵；-C_1-3alkylene-COO-C_2-3-alkylene-N-phthalimide; c_1-3-alkylene-COOCH₂COOR⁵Or C_1-3-alkylene-COOCH₂COR⁶，

Wherein R is⁵Is represented by C_1-4-an alkyl group; c_1-2-an alkoxyethyl group; c_3-4-an alkenyl group; c_3-4-an alkynyl group; a cinnamyl group; a phenoxyethyl group; phenyl-C_1-3An alkyl group; tetrahydro-furfuryl-2; phenyl or by-CH₃、-OCH₃、-COOCH₃or-COOC₂H₅A substituted phenyl group, which is substituted,

R⁶is represented by C_1-4-an alkyl group; phenyl or substituted phenyl, preferably substituted by one or more groups represented by-CH₃、-OCH₃、-OC₂H₅Halogen and-OH,

R²represents H; c_1-6-an alkyl group; substituted C_2-4-alkyl, preferably substituted by one or more groups selected from halogen, -CN, -OH, -OC_1-4-alkyl, -OCOC_1-3-alkyl, -OC₆H₅and-C₆H₅The substituent of the composition; c_3-4-an alkenyl group; substituted C_3-4-alkenyl, preferably substituted by-Cl or-Br; c_3-4-alkynyl, preferably propargyl; c_2-4alkylene-OCO-C_1-3-alkyl or C_1-3alkylene-COO-R⁵，

R³Represents H; CH (CH)₃；-NHCO-A¹or-NHCOO-A²，

Wherein

A¹Represents H; c_1-4-an alkyl group; c_2-3-an alkenyl group; a phenyl group; -NH₂Or substituted C_1-2-alkyl, preferably substituted by one or more groups selected from-OH, -Cl, -OCH₃、-OC₂H₅and-C₆H₅The substituent group of the composition is substituted,

A²is represented by C_1-4-alkyl or substituted C_2-4-alkyl, preferably substituted by one or more of-Cl, -OCH₃and-OC₂H₅Substituent of the composition, and

R⁴represents H; halogen or C_1-4An alkoxy group,

and mixtures thereof.

Another particular preference is given to dyes of the formula (I-B)

Wherein

X represents H; halogen, preferably Cl or Br; -OH; -OCH₃Or NO₂，

Y represents a hydrogen atom (H) or a hydrogen atom (H),

R⁷represents H; a benzyl group; a phenyl group; c_1-6-an alkyl group; substituted C_2-4-alkyl, preferably substituted by one or more groups selected from halogen, -CN, -OH, -OC_1-4-alkyl, -OCOC_1-2-alkyl, -OC₆H₅or-C₆H₅The substituent of the composition; -C_1-2-alkylene-COOC_1-2-an alkyl group; -NHC₆H₅or-NH₂And mixtures thereof.

Another particular preference is given to dyes of the formula (I-C)

Wherein

X represents H; halogen, preferably Cl or Br; -OH; -OCH₃Or NO₂；

Y represents a hydrogen atom (H) or a hydrogen atom (H),

R⁸represents H; c_1-6-an alkyl group; a cyclohexyl group; a phenyl group; substituted phenyl, preferably substituted by one halogen, -CH₃、-CN、-OH、-OC_1-4-alkyl, -OCOC_1-2-alkyl, -COC_1-2-alkyl, -COOH, -SO₂C₂H₄OH or-NO₂The substituent group of the composition is substituted,

R⁹is represented by C_1-4-an alkyl group; phenyl or-CF₃，

And mixtures thereof.

Unless stated to the contrary, any alkyl group when present is linear or branched.

Any substituted alkyl group, when present, may be optionally substituted with one or more substituents which may be the same or different.

The halogen atom is preferably chlorine or bromine.

The above novel compounds and mixtures thereof are very useful disperse dyes.

Preparation of these dyes by diazotisation of the amines of the formula (II)

Wherein all substituents have the meanings given in any of the preceding description, with a compound of the formula (III)

H-K(III)

Wherein all substituents have the meaning as defined above.

For the preparation of cyano derivatives of compound (I), further comprising the steps of: the bromo-derivatives of the compounds of formula (I) wherein X and/or Y represent-Br, are partially or fully cyanated.

Diazotization and coupling are carried out by generally known methods.

The diazotization is carried out, for example, using sodium nitrite in an acidic aqueous medium. Other diazotising agents such as nitrosylsulfuric acid may also be used for the diazotisation. 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 conveniently carried out at a temperature in the range of-10 to 10 c, preferably in the range of 0 c to 5 c.

The coupling reaction of the diazotized compound of the formula (II) with the coupling component of the formula H-K (III) is carried out in a known manner, for example in an acid, aqueous or aqueous-organic medium, preferably at a temperature in the range from 0 ℃ to 50 ℃ and more preferably at a temperature in the range from 10 ℃ to 20 ℃. 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, such as sodium nitrite, which are present in solid form or in the form of an aqueous solution, or in nitrosylsulfuric acid, are used as nitrosating agents. Preparation of diazonium ions, typically by reaction with excess nitrous acid or the like, e.g., nitrosylsulfuric acid, at low temperatures to form electrophilic ion aryl-N₂ ⁺For example, in the literature [ Advanced Organic Chemistry, Fieser&Fieser，pages 736-740]Or [ Organische Chemie, K.Peter C.Vollhardt, pages 1154-]Is disclosed in (1).

Compounds of formula (II) wherein X and Y represent hydrogen are known [ v.f. pozdnev, khimgeosterikl. soedin.1990, 3, 312], the compounds of formula (III) can be readily prepared in a manner familiar to those skilled in the art. Compounds of formula (II) wherein X and/or Y represent a bromo group, may be synthesized according to a method analogous to DE 19643769 a1, example 1. Dyes of formula (I) wherein X and/or Y represent cyano groups can be obtained according to a similar manner to EP 554695 a1, example 1, by replacing bromine with — CN groups.

The novel dyes of the formula (I) and mixtures thereof can be used for dyeing and printing semi-synthetic, preferably synthetic, hydrophobic fibre materials, in particular textile materials. It is also possible to dye textile materials consisting of blend fabrics containing these semi-synthetic hydrophobic fibre materials using the dyes of the present invention.

Suitable semisynthetic textile materials are mainly cellulose-2 * acetate, cellulose triacetate, polyamides and high molecular weight polyesters and mixtures thereof with cellulose.

Synthetic hydrophobic textile materials consist predominantly of linear aromatic polyesters, for example those composed of terephthalic acid and glycols, in particular ethylene glycol, or of condensates of terephthalic acid and 1, 4-bis (hydroxymethyl) cyclohexane; consisting of polycarbonates, such as those consisting of α, α -dimethyl-4, 4' -dihydroxydiphenyl methane and phosgene; and those consisting of fibers based on polyvinyl chloride and polyamide.

The hydrophobic synthetic material can be present in the form of a sheet-like or thread-like structure and can be processed, for example, to a spun or woven, knitted or terry fabric. The novel dyes are also suitable for dyeing hydrophobic synthetic materials in the form of microfibres.

The novel dyes of formula (I) can be conveniently converted into a dye formulation prior to use. This is achieved by grinding the dye to an average particle size of 0.1-10 microns. The milling may be carried out in the presence of a dispersant. Typically, the wet dye is milled with a dispersant, and thereafter dried in vacuum or spray dried. Printing pastes and dye baths may be obtained by adding water to the formulation.

The novel dyes of formula (I) can be applied to textile materials by known dyeing or printing methods, such as those described in french patent application No. 1.445.371.

Typically, polyester fiber materials are dyed from an aqueous dispersion by the exhaust process in the presence of conventional anionic or nonionic dispersants and in the presence or absence of conventional swelling agents (carriers) at temperatures in the range of 65 ℃ to 140 ℃.

Cellulose-2 * -acetate is preferably dyed at a temperature in the range of 65 ℃ to 85 ℃ and cellulose triacetate at temperatures up to 115 ℃. The novel dyes are suitable for dyeing by the hot-melt process, the exhaust process, the continuous process and for printing by modern imaging processes, for example the thermal transfer process, the inkjet printing process, the hot-melt inkjet printing process or the direct printing process.

The thermosol, degas and continuous methods are well known dyeing methods, described for example in m.peterand h.k.rouette: "GrundAgen der Textilveredemount; handbuch der technology, Verfahren und Maschinen', 13th reviewed Edition, 1989, Deutscher Fachverlag GmbH, Frankfurt am Main, Germany, ISBN 3-87150-; of particular interest are the following pages: pages 460-461, pages 482-495, pages 556-566 and pages 574-587.

In ink jet printing, individual droplets of ink are ejected from a nozzle onto a substrate in a controlled manner. Continuous ink jet methods and drop-on-demand methods are mainly used in ink jet printing. In the case of the continuous ink-jet process, the droplets are generated continuously and the droplets not required for printing are transferred to a collecting tank and then recirculated. In contrast, in the case of the discontinuous drop-on-demand method, droplets are generated and printed as needed, i.e., droplets are generated only when printing is needed. The droplets can be generated, for example, by a piezoelectric ink jet head or by thermal energy (bubble jet).

In hot melt inkjet printers, a solid hot melt ink is loaded into a printer in which an inkjet printer head melts the ink, ejecting a liquid ink which rapidly resolidifies upon impact on a substrate. Conventional hot melt ink jet printers have a print head and an ink jet temperature of from about 120 to about 150 c. At that temperature, the solid ink melts into a liquid of low viscosity, typically about 8-25cP when measured at jetting temperatures.

Conventional printing methods are well known, which transfer printing inks or printing pastes onto a substrate in different ways: for example, the ink or paste may be applied by a positive type (e.g. flapper, flexo), from a flat surface (offset), from a concave surface (intaglio), or through a stencil (screen). Different application methods and different substrates require inks of different properties.

The dyeing is carried out by the degassing process in an aqueous liquid and the liquid ratio can be 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. In addition, the dyeing liquor may contain other additives such as dyeing auxiliaries, dispersants, wetting agents and defoamers.

The liquid may also comprise an inorganic acid, such as sulphuric or phosphoric acid, or conveniently an organic acid, such as formic or acetic acid, and/or a salt, such as ammonium acetate, ammonium sulphate or sodium sulphate. The acid is mainly used for adjusting the pH value of the dyeing solution, wherein the pH value of the dyeing solution is preferably in the range of 4-5.

The disperse dyes are usually present in the dyeing liquor in the form of a fine dispersion. Suitable dispersants for preparing such dispersions are, for example, anionic dispersants, such as aromatic sulfonic acid/formaldehyde condensates, sulfonate methoprene oil/formaldehyde condensates, copolymers of lignosulfonates or acrylic acid derivatives, preferably aromatic sulfonic acid/formaldehyde condensates or lignosulfonates, or nonionic dispersants based on polyalkylene oxides, which are obtainable, for example, from ethylene oxide or propylene oxide by polyaddition. Other suitable dispersants are listed in US 4,895,981 or US5,910,624.

Suitable inks or pastes comprise a) a dyeing of at least one compound 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.

The ink or paste preferably comprises the dye of formula (I) above in a total amount of 1 to 35% by weight, especially 2 to 35% by weight, preferably 2 to 30% by weight, more preferably 2.5 to 20% by weight, based on the total weight of the ink or 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, then the dyeing of formula (I) or the mixture thereof is preferably completely dissolved in this medium.

Preferably, the dye of formula (1) or a mixture thereof has a solubility of at least 2.5% by weight in this medium b) at 20 ℃.

When the ink composition of the invention is used for printing paper-like substrates or hydrophobic substrates made of acetate-, polyester-, polyamide-, polyacrylonitrile-, polyvinyl chloride-or polyurethane-polymers and mixtures thereof, the ink is preferably used together with 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 in the range of from 99: 1 to 1: 99, more preferably in the range of from 99: 1 to 50: 50, and particularly preferably in the range of from 95: 5 to 80: 20. The organic solvent included in the aqueous mixture is preferably a water soluble solvent or a mixture of different water soluble solvents. A preferred water-soluble or partially water-soluble organic solvent is C_1-6Alcohols, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanolAlcohols, 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 and thiodiethylene glycol and oligo-and poly-alkylene 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; cyclic 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 combination, medium b) comprises water and at least two or more, more preferably two 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, thiodiethylene glycol, 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.

A preferred medium b) comprises:

(i)75-95 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 patent specifications 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, this solvent has a boiling point of from 30 to 200 ℃, more preferably from 40 to 150 ℃ and particularly preferably from 50 to 125 ℃. 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, inter alia, aliphatic hydrocarbons; esters, preferably ethyl acetate; chlorinated hydrocarbons, preferably CH₂Cl₂(ii) a 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; ketones, preferably methyl ethyl ketone.

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

When it is a mixture of different solvents, it is preferably a mixture comprising 2 to 5 different anhydrous solvents. This makes it possible to provide a medium b) which can control the drying properties and stability of the ink composition well when stored.

Ink compositions comprising an anhydrous organic solvent or mixtures thereof are of particular interest when rapid drying is required, especially when used for printing of hydrophobic and non-absorbing substrates such as plastics, metals and glass.

Preferred low melting point media have a melting point of 60-140 ℃. Useful low melting solid materials include long chain fatty acids or alcohols, preferably having C_18-24-those of carbon chains, and sulfonamides. Conventional low melting ink vehicles typically include various proportions of paraffin wax, resin, plasticizer, binder, viscosity modifier, and antioxidant.

The ink composition and printing paste of the present invention may further include auxiliary components commonly used in inkjet inks or printing pastes, such as buffers, viscosity modifiers, surface tension modifiers, fixatives, accelerating agents, biocides, preservatives, leveling agents, drying agents, humectants, ink penetration additives, light stabilizers, UV absorbers, fluorescent whitening agents, anti-coagulants, ionic or non-ionic surfactants, and conductive salts, as auxiliaries.

These auxiliaries are preferably added to the ink in an amount of 0 to 5% by weight. These auxiliaries are added to the printing pastes in amounts of up to 70% by weight, in particular up to 60% by weight, preferably up to 55% by weight, 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 and cleaned. This can be achieved by generally known purification methods.

When the compositions according to the invention are used for printing textile fibre materials, the following compositions are preferably used.

When printing textile fibre materials, useful additives, in addition to solvents including water, are synthetic, natural or modified natural thickeners which may include water-soluble nonionic cellulose ethers, alginates or bean gum ethers. All water-soluble nonionic cellulose ethers, alginates and bean gum ethers can be used as thickeners to adjust the viscosity of the ink to a certain extent.

Useful water-soluble nonionic cellulose ethers include, for example, methyl-, ethyl-, hydroxyethyl-, methylhydroxyethyl-, hydroxypropyl-or hydroxypropylmethyl-cellulose. Preferred are methylcellulose, especially hydroxyethylcellulose. The cellulose ethers are generally used in amounts of from 0.01 to 2% by weight, in particular from 0.01 to 1% by weight, preferably from 0.01 to 0.5% by weight, based on the total weight of the ink.

Useful alginates include in particular alkali metal alginates, preferably sodium alginate. These are generally used in amounts of from 0.01 to 2% by weight, in particular from 0.01 to 1% by weight, preferably from 0.01 to 0.5% by weight, based on the total weight of the ink. The printing paste comprises up to 70% by weight of thickener, preferably up to 55% by weight of thickener. The thickeners are used in the printing pastes in amounts of from 3 to 70% by weight, in particular from 5 to 60% by weight, preferably from 7 to 55% by weight, based on the total weight of the printing paste.

In the ink jet printing process, the ink composition preferably has a viscosity of from 1 to 40mPa.s, especially from 5 to 40mPa.s, preferably from 10 to 40 mPa.s. Ink compositions having a viscosity of 10 to 35mpa.s are particularly preferred.

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 ink compositions preferably have a conductivity of 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 are sodium acetate, disodium hydrogen di-phosphate, sodium borate, sodium tetraborate and sodium citrate.

The dyeings or prints obtained have good all-round fastness; particularly, it has heat migration fastness, heat fixing fastness and folding fastness, and excellent moisture resistance.

The dyes of the present invention can be used for pigmenting macromolecular organic materials, natural or synthetic, such as plastics, resins, varnishes, paints, electrophotographic toners and developers, electret materials, colour filters and inks, including printing inks, and seeds.

Macromolecular organic materials which can be coloured using the dyes according to the invention include, for example, cellulosic compounds, such as cellulose ethers and esters, for example ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural binders, such as fatty acids, fatty oils, resins and conversion products thereof, or synthetic resins, such as polycondensates, polyadducts, addition polymers and copolymers, for example amino resins, especially urea-and melamine-formaldehyde resins, alkyd resins, acrylic resins, phenolic plastics and phenolic resins, for example novolaks or phenolic resins a, urea resins, vinyl polymers, such as polyvinyl alcohols, polyvinyl acetals, polyvinyl acetates or polyvinyl ethers, polycarbonates, polyolefins, for example polystyrene, polyvinyl chloride, polyethylene or polypropylene, poly (meth) acrylates and copolymers thereof, for example, polymeric alkenoic or polyacrylonitrile, polyamides, polyesters, polyurethanes, coumarone-indene and hydrocarbon resins, epoxy resins, unsaturated synthetic resins (polyesters, acrylates) with different curing mechanisms, paraffin, aldehyde and ketone resins, gums, rubbers and their derivatives and latexes, casein, silicones and silicone resins; individually or in mixtures.

It is not important in this connection whether the macromolecular organic compounds mentioned are present in the form of plastically deformable compositions, melts or in the form of coatings, dispersions, varnishes, paints or printing inks. Depending on the intended use, the dyes according to the invention can advantageously be used in the form of mixtures or formulations or dispersions. The dyes according to the invention are used in amounts of from 0.05 to 30% by weight, preferably from 0.1 to 15% by weight, based on the macromolecular organic material to be pigmented.

In some cases it is also possible to use a correspondingly coarse pigment composition having a BET surface area of more than 2m²A/g, preferably greater than 5m²Per g, rather than grindingAnd/or a polished pigment composition of the present invention. This crude product can be used alone or optionally together with other crude or ready-made pigments to prepare pigment concentrates having a concentration of 5% to 99% by weight in liquid or solid form.

In addition, the dyes of the present invention are useful as colorants in electrophotographic toners or developers, for example, in one-or two-component powder toners (also known as one-or two-component developers), magnetic toners, liquid toners, addition polymerization toners, and other specialty toners.

Typical tinting binders are addition polymerization, polyaddition and polycondensation resins, such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester, phenol-epoxy resins, polysulfones, polyurethanes, which may be used alone or in combination, and polyvinyl phenol-polypropylene, each of which may include other components, such as charge control agents, waxes or flow agents, or may be subsequently modified with these additives.

The dyes of the invention can also be used as colorants in powders and powder coatings, especially tribological or electrostatic sprayable powder coatings for spraying the surface of objects, such as metals, wood, plastics, glass, ceramics, concrete, textile materials, paper or rubber.

The powder coating resins used are typically epoxy resins, carboxyl-and hydroxyl-containing polyester resins, polyurethane resins and acrylic resins together with customary hardeners. Combinations of resins may also be used. For example, epoxy resins are often used in combination with carboxyl-and hydroxyl-containing polyester resins. Typical hardener components (depending on the resin system) include, for example, acid anhydrides, imidazoles, and also dicyandiamide and its derivatives, blocked isocyanates, bisacylurethanes (bisacylurea), phenolic and melamine resins, triglycidyl isocyanurates, oxazolines, and dicarboxylic acids.

The invention also relates to an optical layer comprising at least one dye compound of formula (I) or a mixture thereof. Furthermore, the invention relates to a method for producing an optical layer, comprising the following steps

(a) Providing a substrate

(b) Dissolving a dye compound or a mixture of dye compounds of formula (I) or a mixture thereof in an organic solvent to prepare a solution,

(c) applying solution (b) to substrate (a);

(d) the solvent was removed by evaporation to yield a dyed layer.

Different methods can be used for applying the solution (b) to the substrate (a). To obtain and uniform optical layers, the materials are typically deposited by spin coating, vacuum evaporation, spray coating, roll coating, or dipping.

The organic solvent is selected from C_1-8Alcohol, halogen substituted C_1-8Alcohol, C_1-8Ketones, C_1-8Ether, halogen substituted C_1-4An alkane, or an amide. Preferred is C_1-8Alcohol or halogen substituted C_1-8The alcohol is selected from methanol, ethanol, isopropanol, diacetone alcohol (DAA), 2, 3, 3-tetrafluoropropanol, trichloroethanol, 2-chloroethanol, octafluoropentanol or hexafluorobutanol; preferred is C_1-8The ketone is selected from acetone, methyl isobutyl ketone, methyl ethyl ketone or 3-hydroxy-3-methyl-2-butanone; preferred halogen-substituted C_1-4The alkane is selected from chloroform, dichloromethane or 1-chlorobutane; preferred amides are selected from dimethylformamide or dimethylacetamide.

In a preferred embodiment of the optical layer, the optical layer is an optical data recording layer, which is part of an optical data recording medium.

The structure of optical data recording media is known in the art. Optical data recording media generally comprise a substrate and a recording layer, an optical layer. Generally, a circular or wavy organic polymeric material is used as the matrix. Thus, preferred substrates of the invention are Polycarbonate (PC) or Polymethylmethacrylate (PMMA). The substrate must provide a flat and uniform surface of high optical performance. The optical layer is deposited thereon as a thin and uniform film having high optical properties and a prescribed thickness and finally a reflective layer, such as aluminum, gold or copper, is deposited on the optical layer.

Advanced optical data recording media may further comprise layers such as protective layers, adhesive layers or other optical layers.

For use as an optical data recording layer, spin coating is preferably used to apply the solution (b) to the substrate (a).

The present invention relates to the use of dyes of formula (I) in optical layers for optical data recording, preferably using laser light with a wavelength of up to 500 nm.

The invention also relates to an optical data recording medium of the Write Once Read Many (WORM) type, capable of recording and reproducing information with blue laser radiation, which uses a compound of formula (I) in the optical layer.

In the following examples, parts and percentages are by weight. Temperatures are expressed in degrees celsius.

Example 1

Diazotization:

17.5 parts of 7-amino-4-methylcoumarin are dissolved in 100 parts of water and 36.5 parts of 30% HCl, 75 parts of ice are added and then, over 1 hour, 6.9 parts of sodium nitrite in the form of an aqueous solution (40%) are added at 0 to 5 ℃. The solution is stirred at 0-5 ℃ for 2 hours, and then 0.1 part of sulfamic acid is added to destroy excess sodium nitrite.

Coupling:

the diazonium salt solution prepared previously is added continuously to a solution of 20.6 parts of 1-N-butyl-3-cyano-6-hydroxy-4-methyl-pyridone-2 in 400 parts of water at 15 to 25 ℃. The suspension is stirred at 25 ℃ for 1 hour and the pH is adjusted to 4 by adding 10 parts of 30% sodium hydroxide solution. The suspension was stirred for a further 1 hour, and the precipitated dye was filtered off, washed with water and dried in vacuo at 60 ℃.

Isolating the resulting dye of the formula (IV)

With a lambda of 449nm_max(in DMF) and the polyester was dyed yellow with good fastness.

Example 2

Diazotization:

the diazotization is analogous to the process in example 1.

The diazonium salt solution prepared previously is added continuously to a solution of 10.3 parts of 1-N-butyl-3-cyano-6-hydroxy-4-methyl-pyridone-2 and 9.6 parts of-N-propyl-3-cyano-6-hydroxy-4-methyl-pyridone-2 in 400 parts of water at 15-25 ℃. The suspension is stirred at 25 ℃ for 1 hour and the pH is adjusted to 4 by adding 10 parts of 30% sodium hydroxide solution. The suspension was stirred for a further 1 hour, and the precipitated dye was filtered off, washed with water and dried in vacuo at 60 ℃.

Separated dye mixtures of the formulae (V-A) and (V-B)

With a lambda of 449nm_max(in DMF) and the polyester was dyed yellow with good fastness.

The following tables 1, 2 and 3 give further dyes of the formulae (I-A), (I-B) and (I-C), which are prepared by analogous methods to those given in the preceding examples.

All dyes give very good allround fastness properties, especially fastness to light, sublimation and moisture.

TABLE 1/examples 3 to 31

Example numbering	X	Y	R	R	R	R	λDMF[nm]
								3	H	H	H	H	-CHCH	-CHCH-CN	455
4	H	H	H	-CH	-CHCH	-CHCH-CN	467
								5	H	H	H	-CH	-CH	-CHCH-CN	462
6	H	H	H	H	-CH-CH＝CH	-CHCH-CN	460
								7	H	H	H	H	-CHC≡CH	-CHCH-CN	451
8	H	H	H	H	-CHCH(OH)CH	-CHCH-CN	456
								9	H	H	H	H	-CHCHOCOCH	-CHCHOCOCH	451
10	H	H	H	H	-CHCHCOOCH	-CHCHCOOCH	449
								11	H	H	H	-NHCOCH	-CHCHOCOCH	-CHCHCN	476
12	H	H	H	-NHCOCH	-CHCHOCOCH	-CHCHOCOCH	486
								13	H	H	H	-NHCOCH	-CHCH	-CHCH	506
14	Br	Br	H	-NHCOCH	-CHCH	-CHCH	554
								15	Br	CN	H	-NHCOCH	-CHCH	-CHCH	576

16	H	H	H	-NHCOCH	-CHCH	-CH-CH＝CH	501
								17	H	H	H	-NHCOCH	-CHCH	-CH-CH	499
18	H	H	H	-NHCOCH	-CHCHOCH	-CHCHOCH	502
								19	H	H	H	-NHCOCH	-CHCH	-CHCHOCH	503
20	H	H	H	-NHCOCH	-CHCH	-CHCHCOOCH	498
								21	H	H	H	-NHCOCHCl	-CHCH	-CHCH	502
22	H	H	H	-NHCOCHCHCl	-CHCH	-CHCH	503
								23	H	H	H	-NHCOCOOCH	-CHCH	-CHCH	501
24	H	H	H	-NHCOCOOCH	-CHCH	-CHCH	500
								25	H	H	H	-NHCOCHOCH	-CHCH	-CHCH	503
26	H	H	H	-NHCOCH	-CHCH	-CHCHCOOCHCOOCH	495
								27	H	H	H	-NHCOCH	-CHCH	-CHCHCOOCHCOOCH	496
28	H	H	H	-NHCOCH	-CHCH	-CHCHCOOCHCH	493
								29	H	H	H	-NHCOCH	-CHCH	-CH2CH2COOCH2COCH	490
30	H	H	H	-NHCOCH	-CHCH	-CHCHCOOCH-N-phthalimido group	497
								31	H	H	H	-CH	-CH-CH＝CH	-CHCH-CN	460

TABLE 2/examples 32 to 41

Example numbering	X	Y	R	λDMF[nm]
					32	H	H	-CH	446
33	H	H	-CHCH	448
					34	H	H	-CHCH-CH	449
35	H	H	-CHCHCHCHCHCH	449
					36	H	H	-CHCHCH-O-CHCHCHCH	448
37	H	H	-CH-CH	449
					38	H	H	-CHCH-OH	448
39	H	H	-CHCHCOOCH	449
					40	H	H	-CHCOOCH	449
41	H	H	-NH-CH	449

Example 42

Diazotization:

17.5 parts of 7-amino-4-methylcoumarin are dissolved in 100 parts of acetic acid at 15 ℃ and 17.4 parts of 40% nitrosylsulfuric acid are added over 15 minutes. The solution was stirred at 15 ℃ for 2 hours.

Coupling:

the diazonium salt solution previously prepared is added continuously to a solution of 17.4 parts of 3-methyl-1-phenyl-5-pyrazolone in 100 parts of N-methyl-pyrrolidone and 50 parts of water (containing 0.5 part of sulfamic acid) at 15-25 ℃. The suspension is stirred at 25 ℃ for 1 hour, then 100 parts of ice are added. The suspension was stirred for 30 minutes, the dye suspension was filtered, washed with water and dried under vacuum at 60 ℃.

Isolated dye of the formula (VI)

With a lambda of 411nm_max(in DMF) and the polyester was dyed yellow with good fastness.

TABLE 3/examples 42 to 65

Example numbering	X	Y	R	R	λDMF[nm]
						42	H	H	CH	-CH	411
43	H	H	CH	-CH	413
						44	H	H	CF	-CH	467
45	H	H	CHCHCH	-CH	407
						46	H	H	CH	-H	427
47	H	H	CH	-CH-2-CH	413
						48	H	H	CH	-CH-3-CH	412
49	H	H	CH	-CH-4-CH	414
						50	H	H	CH	-CH-2-OCH	411
51	H	H	CH	-CH-3-OCH	412
						52	H	H	CH	-CH-4-OCH	410
53	H	H	CH	-CH-2-OH	409
						54	H	H	CH	-CH-3-OH	411
55	H	H	CH	-CH-4-OH	412
						56	H	H	CH	-CH-2-COOH	410
57	H	H	CH	-CH-3-Cl	410
						58	H	H	CH	-CH-4-COOCH	412
59	H	H	COOCH	-CH	437
						60	H	H	CH	-CHCHOHCH	405
61	H	H	CH	-CHCHOHCH	407
						62	H	H	CH	-cyclohexyl radical	404
63	H	H	CH	-CH-4-SOCHOH	414
						64	H	H	CH	-CH-4-NO	418
65	H	H	CH	-COCH	435

Application example A

17.5 parts of the dye of example 1 in the form of a moist presscake are wet-milled by a known method together with 32.5 parts of a commercial dispersant based on lignosulfonate and then ground to a powder. 1.2 parts of this dye formulation are added to 2000 parts of demineralized water at 70 ℃ containing 40 parts of ammonium sulfate; the pH of the bath was adjusted to 5 with 85% formic acid. 100 parts of the washed polyester fabric are placed in this dyeing bath, the vessel is closed, the temperature is raised to 130 ℃ within 20 minutes, and the dyeing is continued at this temperature for a further 60 minutes. After cooling, the polyester fabric was removed from the dyeing bath, rinsed, soaped and washed with sodium hydrosulfite in the usual manner by reduction. After heat fixing (180 ℃ C., 30 seconds), yellow colorations having very good all-round fastness properties, in particular light fastness and sublimation resistance, in particular very good wet fastness properties, are obtained. The dyes of examples 2 to 65 can be used in a similar manner to obtain colorations having very good allround fastness properties.

Polyester yarns can be similarly dyed using the dyes of examples 2-65.

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 65 or the dye mixtures of examples 1 to 65 can also be used in a manner analogous to that described in application example B.

Application example C

A printing paste of the present invention is composed of the following components,

500g of thickener (Bean Gum Ether such as Indalca)^TM)，

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

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

10g of buffer and Dispersion for dyeing (e.g.Sandacid PB)^TM；1∶2)，

And

10g of the dye of example 1

Then 1000g with water.

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

The printing pastes are used for printing paper-like substrates, textile fibre materials and plastic films and plastic transparencies.

The dyes of examples 2 to 65 or the dye mixtures of examples 1 to 65 can also be used in a manner analogous to that described in application example C.

Application example D

The polyester interlock knit fabric was printed with a conventional printing press using the printing paste of application example C. 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 and then with demineralized water for 5 minutes. The fibres thus treated contained 4g/l Na₂CO₃2g/l sodium bisulfite (85%) and 1g/l Lyogen DFTTM (trade mark of Clariant AG, Muttenz, Switzerland). A further 15 minutes rinsing with tap water was carried out, followed by a final drying step. This gives a yellow-printed polyester fabric which has good all-round fastness properties, in particular light and sublimation and moisture resistance.

The dyes of examples 2 to 65 or the dye mixtures of examples 1 to 65 can also be used in a manner analogous to that described in application example D.

Application example E

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

Parts of the components of the ink composition

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-like substrates, textile fibre materials and plastic films and plastic transparencies.

The dyes of examples 2 to 65 or the dye mixtures of examples 1 to 65 can also be used in a manner analogous to that described in application example E.

Application example F

The polyester interlock knit fabric was ink jet printed using the printing ink of application example E. The printed fabric was treated using a post-printing treatment method similar to that in application example D. This gives a yellow-printed polyester fabric which has good allround fastness properties, in particular light fastness properties, in particular excellent sublimation fastness properties, in particular excellent wet fastness properties.

The dyes of examples 2 to 65 or the dye mixtures of examples 1 to 65 can also be used in a manner analogous to that described in application example F.

Claims (11)

1. A dye of the formula (I-B)

Wherein

X represents H or a halogen,

y represents a hydrogen atom (H) or a hydrogen atom (H),

R⁷is represented by C_1-6-an alkyl group; substituted C_2-4-alkyl, substituted by one halogen, -OH, -OC_1-4-alkyl or-C₆H₅Taken from the group consisting ofSubstituent groups; -C_1-2-alkylene-COOC_1-2-an alkyl group; -NHC₆H₅or-NH₂，

Or mixtures thereof.

2. A dye or a mixture thereof according to claim 1, wherein X represents H, Cl or Br.

3. A process for the preparation of the dyes of the formula (I-B) according to claim 1, characterized in that: diazotized amines of the formula (II)

Wherein all substituents have the meanings given in claim 1, with compounds of the formula (III)

Wherein all substituents have the meanings given in claim 1.

4. A process according to claim 3, wherein X represents H, Cl or Br.

5. Use of a dye of formula (I-B) or a mixture thereof according to claim 1 or 2 for dyeing or printing fibres or filaments comprising fully synthetic or semi-synthetic hydrophobic organic material or material made therefrom.

6. Use of a dye of formula (I-B) or a mixture thereof according to claim 1 or 2 in an inkjet printing process or a hot melt inkjet process.

7. A composition comprising a dye of formula (I-B) according to claim 1 or 2 or a mixture thereof.

8. The composition of claim 7, wherein the composition is a printing paste or printing ink.

9. The composition of claim 8, wherein the composition is an ink jet printing ink.

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

11. A fibre or filament or a material made therefrom comprising a fully synthetic or semi-synthetic hydrophobic organic material which has been dyed or printed with a dye of formula (I-B) according to claim 1 or 2 or a mixture thereof.