DE102005033584A1 - New heterocyclic dye compounds useful e.g. for coloring and printing natural and synthetic fiber materials, for coloring paper or celluloses in the mass and in the manufacture of magenta color recording fluids - Google Patents

Abstract

Heterocyclic dye compounds (A) are new. Heterocyclic dye compounds (A) of formula (I-VI), are new. R1, R2 : OH, O(1-6C alkyl), O(1-6C alkyl)-COOM, O(1-6C alkyl)-SO3M, SH, S(1-6C alkyl), S(1-6C alkyl)-COOM, S(1-6C alkyl)-SO3M, SO3M, SO2NH2, SO2N(hydroxy(1-6C alkyl))2, SO2NH(1-6C alkyl), SO2N(1-6C alkyl)2, NH2, NH(1-6C alkyl), NH-acyl, NH-aryl, N(1-6C alkyl)2, NH(1-6C alkyl)-COOM, NH(1-6C alkyl)-SO3M, where the alkyl- and/or aryl residue is substituted with OH, halo, NH2, SO3M, COOM or SO2NH2; and M : H, univalent metalcation, equivalent and polyvalent metalcations or ammonium ion optionally substituted with alkyl, alkoxyalkyl or hydroxyalkyl. Independent claims are included for: (1) the preparation of (I) to (III); (2) the preparation of (IV) to (VI); and (3) a recording fluid containing (A) optionally in combination with a shading dye. [Image] [Image] [Image] [Image] [Image] [Image].

Description

The The present invention describes the use of modified ones Reactive dyes as a coloring component in recording fluids and inks, especially for the inkjet process (ink jet printing), as well as a colorant for electrophotographic Toner, powder coatings and color filters.

At the Inkjet process is a non-contact Printing process, which is generally between two printing techniques different: Drop-On-Demand and Continuous Stream. The drop-on demand Principle is based on that the ink in the form of a drop a nozzle placed in the right place at the right time, whereas at the right time Continuous stream the ink permanently and then either on the recording medium, e.g. Paper, hitting or distracted into a containment container becomes. To prints of high sharpness and good resolution to receive the recording fluids and the dyes contained therein meet certain requirements, in particular with regard to impurities used in the manufacture of Inks used in dye solutions the stability the inks can affect what to agglomeration or even precipitation of the dye can. To blockages in the nozzles and deposits (kogation) in printheads of recording machines or to avoid printers due to contamination or foreign matter, have to the recording fluids or the inks meet the requirements. The most important role comes while the dyes used in the inks. Especially Impurities of anions in the dye solutions, such as chloride or sulfate, can too Difficulty printing or stability problems with the inks to lead.

When standard magenta dyes for ink-jet printing currently mainly C.I. Acid Red 52, Reactive Red 180, Reactive Red 195 (EP-A-0 613 975) and Reactive Red 241 (EP-A-1 281 738). Except for Acid Red 52, these are reactive dyes, in the for Inks usually alkaline environment sulphate or Chloride ions release, leading to precipitation in the ink and to Clogging or corrosion of the printhead can result.

Description of the invention

Surprisingly It was found that by reaction of the Reactive Red 195 and the Reactive Red 241 with appropriate nucleophiles a partial or fully unreactive form of these dyes can be obtained Sulfate or chloride ions no longer or only under drastic Conditions such as high pH and / or high temperature release can. This is very cost effective magenta dyes with good light fastness and high brilliance for inks and recording fluids available, the additionally over one good storage stability in an alkaline environment.

worin
R¹ oder R² unabhängig voneinander OH, O(C₁-C₆)-Alkyl, O(C₁-C₆)-Alkyl-COOM, O(C₁-C₆)-Alkyl-SO₃M, SH, S(C₁-C₆)-Alkyl, S(C₁-C₆)-Alkyl-COOM, S(C₁-C₆)-Alkyl-SO₃M, SO₃M, SO₂NH₂, SO₂N(Hydroxy(C₁-C₆)-Alkyl)₂, SO₂NH(C₁-C₆)-Alkyl, SO₂N((C₁-C₆)- Alkyl)₂, NH₂, NH(C₁-C₆)-Alkyl, NNAcyl, NHAryl, N((C₁-C₆)-Alkyl)₂, NH(C₁-C₆)-Alkyl-COOM, NH(C₁-C₆)-Alkyl-SO₃M darstellt,
der Alkyl- bzw. der Arylrest seinerseits mit OH, Halogen, NH₂, SO₃M, COOM, SO₂NH₂ substituiert sein kann und
M für Wasserstoff, ein einwertiges Metallkation, ein Äquivalent eines mehrwertigen Metallkations oder ein gegebenenfalls mit Alkyl, Alkoxyalkyl oder Hydroxyalkyl substituiertes Ammoniumion steht. The invention relates to the following dyes having the general formula 1 to 6,

wherein
R ¹ or R ² independently of one another are OH, O (C ₁ -C ₆ ) -alkyl, O (C ₁ -C ₆ ) -alkyl-COOM, O (C ₁ -C ₆ ) -alkyl-SO ₃ M, SH, S (C ₁ -C ₆ ) alkyl, S (C ₁ -C ₆ ) alkyl COOM, S (C ₁ -C ₆ ) alkyl SO ₃ M, SO ₃ M, SO ₂ NH ₂ , SO ₂ N (hydroxy (C ₁ -C ₆ ) alkyl) ₂ , SO ₂ NH (C ₁ -C ₆ ) alkyl, SO ₂ N ((C ₁ -C ₆ ) alkyl) ₂ , NH ₂ , NH (C ₁ -C ₆ ) -alkyl, NNAcyl, NHAryl, N ((C ₁ -C ₆ ) -alkyl) ₂ , NH (C ₁ -C ₆ ) -alkyl-COOM, NH (C ₁ -C ₆ ) -alkyl SO ₃ M represents,
the alkyl or aryl radical may in turn be substituted by OH, halogen, NH ₂ , SO ₃ M, COOM, SO ₂ NH ₂ and
M is hydrogen, a monovalent metal cation, one equivalent of a polyvalent metal cation or an optionally substituted with alkyl, alkoxyalkyl or hydroxyalkyl ammonium ion.

The Dyes of the formulas 1 to 3 are obtained in an aqueous medium by reaction from Reactive Red 195 or Reactive Red 241 with suitable inorganic Bases. The dyes of the general formulas 4 to 6 are obtained by Implementation of Reactive Red 195 or Reactive Red 241 with the corresponding Nucleophiles of the formula H-R1 and / or H-R2 in the presence of suitable inorganic or organic bases. Suitable inorganic bases For example, lithium hydroxide, lithium carbonate, sodium hydroxide, Sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, Potassium bicarbonate and ammonia. Suitable organic bases are, for example, monoethanolamine, diethanolamine, triethanolamine, 2-aminopropanol, 3-aminopropanol, dipropanolamine, tripropanolamine, N-methylaminoethanol, N, N-dimethylaminoethanol, N-phenylamino-propanol, Ethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, Tetramethylhexylenediamine, diethylenetriamine, triethylenetetramine, Triethylamine, diisopropylethylamine and polyethyleneimine.

The Reactions are preferred at temperatures of 0 to 100 ° C at 20 to 80 ° C, particularly preferably at 40 to 60 ° C, and at pH values of 6 to 12, preferably 8 to 10 carried out. to complete implementation The mixtures are stirred for 0.5 to 10 h, preferably 2 to 6 h.

The dyes of the invention can from the first obtained, preferably aqueous Reaction mixtures, by salting out, filtration or by spray drying, optionally after partial or complete desalination by membrane filtration, be isolated. However, it can also be dispensed with insulation are, and containing the dyes of the invention Reaction mixtures can by Addition of organic and / or inorganic bases and / or humectants and optionally after partial or complete desalination by membrane filtration be transferred directly into concentrated dye solutions. Alternatively, the Dyes as a press cake (optionally also in flushing) or as Powder can be used.

object The present invention also relates to the use of the dyes according to the invention To dye and printing on natural and synthetic fiber materials (e.g., polyester, silk, wool, blended fabrics), in particular for recording text and images on different Recording media, as well as for dyeing of paper or pulp in bulk.

The dyes of the invention are particularly suitable for the production of magenta recording fluids, especially of inks on aqueous and non-aqueous base for the ink-jet printing process, as well as for those inks that after the Hot-melt processes work or are based on microemulsions, but also for other printing, duplication, Marking, writing, drawing, stamping or registration procedure.

Furthermore the dyes of the invention are suitable also for coloring of organic and inorganic materials.

object The present invention also relates to recording fluids, which are characterized in that they contain the dyes according to the invention, optionally together with other water-soluble dyes for shading, contain. The exact composition of the recording fluid must be adapted to the intended use.

The manufacture recording fluids generally contain from 0.1 to 50% by weight of the dye according to the invention, 0 to 99 wt .-% water and 0 to 99 wt .-% organic solvent and / or Humectant. In a preferred embodiment, the recording fluids contain 1.0 up to 30% by weight of dye, 70 to 95% by weight of water and 0 to 20% by weight organic solvent and / or Humectant, in another preferred embodiment 1.0 to 30% by weight of dye, 0 to 20% by weight of water and 70 to 95 Wt .-% organic solvent and / or Humectant. The finished recording fluids can still further, mentioned below additions contain.

Water used to make the recording liquids is preferably used in the form of distilled or demineralized water. The solvents and / or humectants contained in the recording fluids may be an organic solvent or a mixture of such solvents, with water-miscible solvents being preferred. Suitable solvents are, for example, monohydric or polyhydric alcohols, their ethers and esters, for example methanol, ethanol, propanol, isopropanol, butanol, isobutanol; dihydric or trihydric alcohols, in particular having 2 to 6 C atoms, for example ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6- Hexanetriol, glycerol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol; lower alkyl ethers of polyhydric alcohols, for example ethylene glycol monomethyl, -ethyl or -butyl ether, triethylene glycol monomethyl or -ethyl ether; Ketones and ketone alcohols such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol; Amides, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; also urea, tetramethylurea, thiodiglycol, ε-caprolactam.

Further can the recording fluids according to the invention still common Additives, such as preservatives, cationic, anionic or nonionic surfactants (surfactants and wetting agents), as well as viscosity modifiers, e.g. Polyvinyl alcohol, cellulose derivatives or water-soluble natural or artificial Resins as film formers or binders for increasing the adhesion and abrasion resistance.

amines, such as Ethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, Diisopropylamine are mainly used for adjusting the pH of the recording liquid. They are usually 0 to 10% by weight, preferably 0.5 to 5 wt .-% in the recording liquid available.

The recording fluids for the Ink-jet printing can depending on the embodiment of the printing process, e.g. as continuous-jet, intermittent-jet, impulse-jet or compound jet processes, still other additives, e.g. for buffering the pH, for adjusting the electrical conductivity, the specific heat, the thermal expansion coefficient and the conductivity, be added.

The Inventive recording liquids are for Thermal and piezo print heads suitable.

Of the Printing the recording fluids of the invention leads to a printed image with high brilliance and good light and water fastness.

at the storage of recording fluids according to the invention occurs no deposition of precipitation, which blurred Print images or clogging of nozzles leads.

The Inventive recording liquids are in terms of viscosity and surface tension in the for Ink-jet process appropriate areas. They deliver print images high optical density with good light fastness, waterfastness, Abrasion resistance and dissolution.

object The invention are further fields of application.

For example are the dyes of the invention suitable as colorants in electrophotographic toners and developers, such as. One-component and two-component powder toners, magnetic toners, liquid toners, Polymerization toners and other special toners.

typical Toner binders are polymerization, polyaddition and polycondensation resins, such as styrene-styrene-acrylate, styrene-butadiene, acrylate, polyester, Phenolic epoxy resins, polysulfones, polyurethanes, alone or in combination, as well as polyethylene and polypropylene, which contain other ingredients, such as charge control agents, waxes or flow agents may contain or can be added afterwards.

Of others are the dyes of the invention suitable as a colorant in powder and powder coatings, in particular in triboelectrically or electrostatically sprayed powder coatings, the surface coating of objects from, for example, metal, wood, plastic, glass, ceramics, concrete, Textile material, paper or rubber are used.

When Powder coating resins are typically epoxy and carboxyl resins hydroxyl-containing polyester resins, polyurethane and acrylic resins along with usual hardeners used. Combinations of resins are also used. So for example, they are common Epoxy resins in combination with carboxyl- and hydroxyl-containing Polyester resins used.

In the described application areas, the dye mixture of the invention also in a mixture with other dyes and / or pigments be used.

In In the following examples, percentages are percentages by weight and (a / a) area percent in the HPLC diagram.

Synthetic Example 1

7.5 g of ^® Evermax Red SF-B (CI Reactive Red 195) in a HPLC purity of 67% (a / a) are dissolved in 42.5 ml of water and the pH is adjusted to 8 with 10% sodium hydroxide solution. The mixture is warmed to 60 ° C and stirred for 2 h. The pH is maintained by adding 10% sodium hydroxide solution. Thereafter, the pH is adjusted to pH 5 with acetic acid.

Of the Dye of formula 1 (sulfovinyl in the meta position) is in HPLC purity of 81% (a / a).

To another 6h at 80 ° C receives a mixture of the dyes of the formula 2 and 3 (Sulfoethylhydroxidrest each in the meta position) in an HPLC purity of 39% (a / a) and 21% (a / a).

Synthesis Example 2

70 g ^® Drimarene Red CI-5B (contains about 10% CI Reactive Red 241) in a HPLC purity of 62% (a / a) are introduced and the pH adjusted to 8 with 20% sodium hydroxide solution. The mixture is warmed to 60 ° C and stirred for 2 h. The pH is maintained by adding 20% sodium hydroxide solution. Thereafter, the pH is adjusted to pH 5 with acetic acid. The solution is filtered off from insoluble constituents and then desalted via membrane demineralization and concentrated to a solids content of 15%.

Of the Dye of formula 1 (sulfovinyl in the para position) is in HPLC purity of 69% (a / a).

Synthesis Example 3

50 g ^® Drimarene Red CI-5B (contains about 10% CI Reactive Red 241) in a HPLC purity of 62% (a / a) are introduced and the pH adjusted to 10 with 20% sodium hydroxide solution. The mixture is warmed to 80 ° C and stirred for 2 h. The pH is maintained by adding 20% sodium hydroxide solution. Thereafter, the pH is adjusted to pH 5 with acetic acid. The solution is filtered off from insoluble constituents and then desalted via membrane demineralization and concentrated to a solids content of 15%.

A Mixture of the dyes 2 and 3 (Sulfoethylhydroxidrest respectively in para-position) are obtained in an HPLC purity of 36% (a / a) and 29% (a / a).

Synthesis Example 4

50.0 g of solution from Synthesis Example 2 in an HPLC purity of 64% (a / a) are introduced and the pH is adjusted to 12 with 1.0 g of 2-monoaminoethanol. The mixture is stirred overnight at 20 ° C. The dye of formula 5 (sulfoethyl-2-hydroxyamine in the meta position with R2 = NHCH ₂ CH ₂ OH) is obtained in an HPLC purity of 65% (a / a).

example

With 30 g of the prepared dye solution from Synthesis Example 1 is replaced by the addition of 20 g of diethylene glycol, 0.5 g of n-butanol, 10 glycerol and 39.5 g of demineralized water, which is printed on plain paper on a Canon S560. You get one magenta print with high brilliance and good lightfastness (4 on the blue wool scale).

Table 1: colorimetric values

Claims (7)

Dyes of the general formula 1 to 6,

wherein R ¹ or R ² independently of one another are OH, O (C ₁ -C ₆ ) -alkyl, O (C ₁ -C ₆ ) -alkyl-COOM, O (C ₁ -C ₆ ) -alkyl-SO ₃ M, SH , S (C ₁ -C ₆ ) -alkyl, S (C ₁ -C ₆ ) -alkyl-COOM, S (C ₁ -C ₆ ) -alkyl-SO ₃ M, SO ₃ M, SO ₂ NH ₂ , SO ₂ N (hydroxy (C ₁ -C ₆₎ -alkyl) _2, SO ₂ NH (C ₁ -C ₆₎ -alkyl, SO ₂ N ((C ₁ -C ₆₎ alkyl) _2, NH _2, NH ( C ₁ -C ₆ ) -alkyl, NHAcyl, NHAryl, N ((C ₁ -C ₆ ) -alkyl) ₂ , NH (C ₁ -C ₆ ) -alkyl-COOM, NH (C ₁ -C ₆ ) -alkyl -SO ₃ M, the alkyl or the aryl radical may in turn be substituted by OH, halogen, NH ₂ , SO ₃ M, COOM, SO ₂ NH ₂ and M is hydrogen, a monovalent metal cation, one equivalent of a polyvalent metal cation or an optionally substituted with alkyl, alkoxyalkyl or hydroxyalkyl ammonium ion. Process for the preparation of the dyes of the formulas (1) to (3) according to claim 1, characterized in that C.I. Reactive Red 195 or 241 is reacted with an inorganic base. Process for the preparation of the dyes of the formulas (4) to (6) according to claim 1, characterized in that C.I. Reactive Red 195 or 241 with a nucleophile of the formula H-R1 and / or H-R2 is reacted in the presence of a base. Method according to claim 2 or 3, characterized that the reaction at a pH between 6 and 12, preferably 8 and 10, performed becomes. Use of the dyes according to claim 1 for dyeing and Printing on natural and synthetic fiber materials and for dyeing paper or pulps in the crowd. Use according to claim 5 for the preparation of magenta Recording fluids, especially of inks on aqueous and non-aqueous base for the ink-jet printing process, as well as for those inks that after the Hot-melt processes work or are based on microemulsions. Recording liquid containing a dye according to claim 1, optionally in combination with a nuancing dye.