EP3116856A1

EP3116856A1 - Novel pyridone dyes

Info

Publication number: EP3116856A1
Application number: EP15710105.6A
Authority: EP
Inventors: Gerald Engel; Yvonne KAHLE; Andreas Endres
Original assignee: Clariant International Ltd
Current assignee: Clariant International Ltd
Priority date: 2014-03-08
Filing date: 2015-03-05
Publication date: 2017-01-18
Also published as: KR20160130826A; US20170015829A1; WO2015135633A1; JP2017513966A; TW201602082A; CN106458906A; DE102014003307A1

Abstract

The invention relates to compounds of formula (I), wherein R⁰ represents C₁-C₆-alkyl or CF₃; R¹ represents sulfo, carboxy, C₁-C₄-alkylene-sulfo, C₁-C₄-alkylene-carboxy, CONH₂, CONH(C₁-C₄-alkyl) or CN, R² represents C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, hydroxy-C₁-C₁₈-alkyl or -(C₁-C₆-alkylene-O-)_m-R, wherein R represents H, C₁-C₁₆-alkyl or hydroxy-C₁-C₁₆-alkyl and m is an integer between 1 to 20, R³H, sulfo, carboxy, C₁-C₆-alkyl or C₁-C₆-alkoxy, R⁴H, C₁-C₆-alkyl or C₁-C₆-alkoxy, R⁵OH, OM, C₁-C₆-alkyl, unsubstituted C₆-C₁₀-aryl or C₆-C₁₀-aryl substituted by C₁-C₆-alky|, halogen, e.g., F, Cl, Br, carboxy or sulfo, wherein the compound of formula (I) contains at least one anionic group from the group of sulfo and carboxy with the counter cation M⁺, wherein M⁺ represents an alkali metal cation or an organic cation. Compounds of formula (I) are especially suited for use in color filters.

Description

New pyridone colorants

The present invention relates to novel colorants used, for example, in color filters for liquid crystal displays or in OLED displays.

Liquid crystal displays are widely used in e.g.

Televisions, PC monitors, mobile phones and tablet computers.

The function of liquid crystal displays (LCDs) is based on the following principle: light shines through first a polarizer, then a liquid crystal layer and then a second polarizer. By

suitable electronic control and alignment of the liquid crystals by means of thin-film transistors, these change the direction of rotation of the polarized light, whereby the brightness of the light emerging from the second polarizer and thus out of the device can be controlled.

In the case of colored LCD displays, color filters are additionally introduced into the arrangement between the polarizers.

These color filters are usually on the surface of a

transparent substrate, usually made of glass, and there are in the form of numerous regularly arranged pixels of primary colors, eg. B. red, green, blue (R, G, B) applied. The single pixel has a size of a few micrometers to 100 micrometers.

In addition to the components mentioned above, a liquid crystal display also has numerous other functional components such as thin-film transistors (TFT), alignment layers and others involved in the control of the liquid crystals and thus ultimately the imaging.

If light now passes through the arrangement, the liquid crystals can be set separately for each pixel by electronic control to "light" or "dark" (or to any intermediate stage). Accordingly, the respective associated color filter pixels are supplied with light and for the

human eye results in the top view of the screen

CONFIRMATION COPY corresponding R, G, B building, colored, moving or still image.

Various ways of arranging liquid crystals, electronic controls and polarizers are known, such as twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA) and in-plane switching (IPS).

Furthermore, the color filter pixels may be arranged in different defined patterns for each base color. The basic colors are present as separate color points next to each other and result from backlit a full color image. In addition to the use of the three primary colors red, green and blue, the use of an additional color, for example yellow, for expanding the color space or the use of cyan, magenta and yellow as primary colors is also known.

In the case of OLED displays, so-called W-OLED displays also use color filters. These displays first generate a white light from pixels of organic light emitting diodes (Organic Light Emitting Diodes), which is then split using color filters in individual colors, for example red, green and blue.

Certain requirements are placed on the color filters: in the manufacture of the liquid crystal displays, elevated process temperatures of typically 230 ° C are used during the application of the liquid crystal control transparent electrode and the orientation layer. Accordingly, the color filters used must have high heat stability.

Further important requirements are, for example, a high contrast ratio, a high brightness of the color filter and the best possible color tone.

A high contrast ratio affects the quality of the image positively. For measuring the contrast ratio, the light intensity becomes after irradiation a color filter on a transparent substrate, where the substrate is between two polarizers. The contrast ratio, also known as the contrast value, indicates the ratio of the light intensities in parallel and perpendicular polarizers.

Light intensity (parallel)

KV = -

Light intensity (perpendicular

A high transmission and resulting brightness of the color filter is desirable because it requires less light to be radiated into the display to produce the same image brightness than a less bright color filter, allowing for overall energy savings.

The requirements for the colorants used in the color filters are constantly increasing.

Even the commercially available commercial products do not always meet all the requirements of technology. In particular, there is a need for improvement with regard to the heat stability, the contrast values and the brightness of the colorants used without any negative influence on chroma and hue. It is desirable in the case of dyes, a good solubility of the colorant in the

Application system. It was a further object to provide greenish yellow colorants with good heat stability for color filter applications.

Surprisingly, it has now been found that new colorants of the general

Formula (I) are well suited for use in color filters. They usually have a good solubility in the solvents typically used.

Likewise, in colorations they show brilliant greenish yellow shades with high color strength. They lead to advantageous application technology

Features such as high brightness and high contrast in the color filter.

The invention relates to compounds of the formula (I), their preparation and use, in particular for dyeing transparent systems. The compounds of the formula (I) have the following general formula:

wherein

R ° d-Ce-alkyl or CF ₃ ;

R ^{1 is} sulfo, carboxy, C ₄ -C ₄ -alkylene-sulfo, C ¹ -C ₄ -alkylene-carboxy, CONH ₂ ,

CONH (dC ₄ -alkyl) or CN,

R ^{2 is} C 1 -C ₆ -alkyl or - (C ₁ -C ₆ -alkylene-O-) _m -R, where R is H or C ₁ -C ₆ -alkyl and m is a number from 1 to 20,

R ^{3 is} H, sulfo, carboxy, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy,

R ^{4 is} H, d-Ce-alkyl or CC ₆ -alkoxy,

R ^{5 is} OH, OM, Ci-Ce-alkyl, unsubstituted or by d-Ce-alkyl, halogen, z. B. F, Cl, Br, carboxy or sulfo substituted C ₆ -C ₀ aryl

mean, wherein the compounds of formula (I) at least one anionic radical from the group sulfo and carboxy, preferably sulfo, with the

Counter cation M ⁺ , wherein M ^{+ is} an alkali metal cation, such as Li +, Na + or K +, or preferably an organic cation, in particular an organic ammonium cation or an organic phosphonium cation means. It is also possible that the counter cation M ^{+ is} a mixture of the aforementioned cations.

The alkylene groups and the alkyl groups in the alkyl and alkoxy radicals are branched or linear. Examples of alkyl groups are methyl, ethyl, propyl, iso-propyl, butyl, preferably n-butyl and iso-butyl, pentyl, preferably n-pentyl and iso-pentyl, hexyl, octyl, ethylhexyl. The C ₁ -C ₆ -alkylene-O groups in the radical - (C ₁ -C ₆ -alkylene-O-) _m -R may be the same or different when m is greater than 1.

Preferred radicals R ° have the meaning CC ₂ alkyl, very particularly preferably methyl.

Preferred radicals R ¹ have the meaning dC ₂ -alkylene-sulfo, CONH (C ₁ -C ₂ -alkyl) or CONH ₂ , particularly preferably C ₁ -C ₂ -alkylene-sulfo, CONHid-C 1 -C 4 -alkyl or CONH ₂ , very particularly preferably CH ₂ sulfo or CONH ₂ .

Preferred radicals R ² have the meaning Ci-C _8- alkyl, hydroxy-CiC ₈ -alkyl or - (CiX-alkylene-O-Jm-R, wherein R has the meaning H or Ci-Ci ₀ -alkyl and m is a number from 1 to 15, in particular ethyl, hydroxyethyl or - (C 1 -C 3 -alkylene-O-) _m -R, where R is H or C 1 -C ₈ -alkyl and m is a number from 1 to 15, completely particularly preferably ethyl or - (C ₂ -C ₃ -alkylene-O-) _m -R, where R is H or methyl and m is a number from 1 to 12.

Preferred radicals R ³ have the meaning H, sulfo, C 1 -C ₄ -alkyl or C 1 -C ₄ -alkoxy, in particular H, methyl, methoxy or sulfo, very particularly preferably H or methyl.

Preferred radicals R ⁴ have the meaning H, C 1 -C ₄ -alkyl or C 1 -C ₄ -alkoxy, in particular H, methyl or methoxy, very particularly preferably H.

Preferred radicals R ⁵ are OH, O ^" M ⁺ , C 1 -C ₄ -alkyl, a phenyl which is substituted by C 1 -C ₂ -alkyl, halogen, for example F, Cl, Br or sulfo, or

unsubstituted phenyl, in particular OH, O ^" M ⁺ , C ₁ -C ₂ -alkyl, a C ₁ -C ₂ -alkyl, chlorine or sulfo-substituted phenyl or an unsubstituted phenyl, very particularly preferably OH, O ^" M ⁺ , methyl, tolyl or phenyl, where M ^{+ is} one

Alkali metal cation, a primary, secondary, tertiary or quaternary

Ammonium ion or a phosphonium ion means. In preferred compounds of the general formula (I)

R ° C ₁ -C ₂ -alkyl, in particular methyl,

R ^{1 is} CC-alkylene-sulfo, CONH (C ¹ -C ₂ -alkyl) or CONH ₂ , in particular C ₁ -C ₂ -alkylene-sulfo, CONH (C ₁ -C ₂ -alkyl) or CONH ₂ ,

R ² is d-Cs-alkyl, hydroxy-dC ₈ -alkyl or - (C ₁ -C ₄ -alkylene-O-) _m -R, where R is the

Meaning H or Ci-Ci _0- alkyl has and

m is a number from 1 to 15,

R ^{3 is} H, sulfo, C 1 -C ₄ -alkyl or C -C -alkoxy,

R ^{4 is} H, CC ₄ -alkyl or C 1 -C ₄ -alkoxy,

R ⁵ OH, O ^~ M \ CC ₄ alkyl, one with Ci-C ₂ alkyl, halogen, eg F, Cl, Br, or

Sulfo-substituted phenyl or unsubstituted phenyl,

where the compounds of the formula (I) have at least one sulfo group,

preferably 1

or 2 sulfo groups, and the counter cation M ^{+ is} as defined above.

In more preferred compounds of the general formula (I)

R ° methyl,

R ¹ is d-Ca-alkylene-sulfo, CONH (dC ₂ -alkyl) or CONH ₂ ,

R ^{2 is} ethyl, hydroxyethyl or - (dC ₃ -alkylene-O-) _m -R, where R is H or C ₁ -C 8 -alkyl and

m is a number from 1 to 15,

R ^{3 is} H, methyl, methoxy or sulfo,

R ^{4 is} H, methyl or methoxy,

R ^{5 is} OH, O ^" M ⁺ , C ₁ -C ₂ -alkyl, a phenyl or unsubstituted phenyl substituted by C ₁ -C ₂ -alkyl, chlorine or sulfo,

wherein the compounds of formula (I) contain 1 or 2 sulfo groups and the

Counter cation M ⁺ as defined above. In particularly preferred compounds of the general formula (I), R ° is methyl,

R ^{1 is} CH ₂ -sulfo or CONH ₂ , R ^{2 is} ethyl or - (C ₂ -C 3 -alkylene-O-) _m -R, where R is H or methyl and

m is a number from 1 to 12,

R ^{3 is} H or methyl,

R ⁴ H,

R ^{5 is} OH, ΟΊνΓ, methyl, tolyl or phenyl,

wherein the compounds of the formula (I) contain 1 or 2 sulfo groups, in particular 1 sulfo group, and the counter cation M ^{+ is} as defined above.

Example of a particularly preferred compound is (IIa)

In all of the above-described compounds of the formulas (I) and (IIa) according to the invention, the counter cation M ^{+ is} preferably an organic cation from the group of imidazolium cations, alkylguanidinium cations,

Phosphonium cations, primary, secondary, tertiary or quaternary

Ammonium ions, benzotriazolyl cations and pyridinium cations.

The imidazolium cations preferably have the general formula (C1):

wherein

R ¹ is d-Cis-alkyl, hydroxy-C ₁ -C ₈ -alkyl, C ₂ -C ₁₈ -alkenyl,

where R has the meaning H, Ci-Ci ₆ -alkyl or hydroxy-Ci-C _16- alkyl and m is a number from 1 to 20, C ₆ -C ₀ aryl, or C ₆ -Cio-aryl substituted by

1, 2 or 3 dC ₄ -alkyl radicals is substituted,

R ² is C ₁ -C ₁₈ -alkyl, hydroxy-C ₁ -C ₈ -alkyl, C ₂ -d ₈ -alkenyl, - (C ₁ -C ₆ -alkylene-O-) _m -R, where R is H, C 1 -C ₆ -alkyl or hydroxy-Ci-Ci ₆ alkyl and m is a number from 1 to 20, C ₆ -C ₁₀ aryl or C ₆ -C ₁₀ aryl, by

1, 2 or 3 d-C-alkyl radicals is substituted,

R ^{3 is} H or methyl.

Particularly preferred are imidazolium cations of the formula (C1) in which R ¹ and R ^{2 are} identical or different and C ₄ -C 12 -alkyl, - (C ₁ -C ₃ -alkylene-O-) _m -R, where R is H, Ci-Ci2-alkyl or hydroxy-Ci-Ci ₂ -alkyl and m is a number from 1 to 3, phenyl or di (isopropyl) phenyl, and R ^{3 is} hydrogen or methyl. Very particularly preferred are imidazolium cations of the formula (C1) in which R ¹ and R ^{2 are} identical or different and C 6 -C 12 -alkyl, - (C ₂ -C ₃ -alkylene-O-) m R, where R is C -C -alkyl ₂ alkyl and m is the number 1; or phenyl or di (isopropyl) phenyl, and R ^{3 is} hydrogen or methyl. The alkylguanidinium cations preferably have the general formula (C2):

wherein

R> 1, D R2, n R3, and n R4 are the same or different and Ci-C ₄ alkyl, preferably

Methyl or ethyl, and

R ⁵ and R ^{6 are} identical or different and C 1 -C ₈ -alkyl, hydroxy-d-

C ₁₈ -alkyl, C ₂ -Ci8-alkenyl, - (dC ₆ -alkylene-O-) _m -R, or C ₆ -C ₀ -aryl, preferably C ₆ -C ₂ -alkyl or phenyl wherein R is H, C 1 -C ₆ -alkyl or hydroxy-C 1 -C ₆ -alkyl and

m is a number from 1 to 20. The phosphonium cations preferably have the general formula (C3):

wherein

R ^{1 is} C ¹ -C ₆ -alkyl or hydroxy-C ¹ -C ₆ -alkyl,

R ^{2 is} C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, hydroxy-d-Ce-alkyl or C ₆ -C ₁₀ -aryl,

R ³ Ci-C ₂ -alkyl, C ₂ -C ₂ o-alkenyl, hydroxy-dC ₂₀ alkyl, C ₆ -C ₁₀ aryl, - (dC ₆ - alkylene-O-) _m -R,

in which

R is H, C 1 -C ₆ -alkyl or hydroxy-C 1 -C ₆ -alkyl and

m is a number from 1 to 20,

R ⁴ dC ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, _{hydroxy-Ci-C2o-alkyl,} C ₆ -C ₀ -aryl, - (dC ₆ - alkylene-0-) _m -R,

wherein R has the above meaning. Particular preference is given to phosphonium cations of the formula (C3)

wherein

R ¹ , R ² and R ^{3 are the} same or different and are C 1 -C 4 -alkyl or phenyl, and

C ₆ -C 8 -alkyl or phenyl.

The organic ammonium cations are primary, secondary, tertiary or quaternary ammonium cations and preferably have the general formula (C4):

wherein

R, R ² , R ³ and R ^{4 are the} same or different and are hydrogen, (dC ₃₀ ) -

Alkyl, (C ₂ -C ₃ o) -alkenyl, hydroxy (C ₁ -C ₃₀ ) -alkyl, C ₁ -C 4 -alkylene-phenyl, (C ₆ -C ₁₀ ) -aryl, C ₁ -C ₆ -alkylene-OCOR ⁵ , where R ^{5 is} C _{6 is} - C ₂₀ alkyl or C ₆ -C ₂₀ alkenyl; - (dC ₆ -alkylene-O-) _m -R, where R is H, d-de-alkyl or

Hydroxy-Ci-d6-alkyl and m is a number from 1 to 20,

with the proviso that the sum of the carbon atoms in the radicals R ¹ to R ^{4 is} at least 6, preferably at least 8, in particular at least 12, particularly preferably at least 16.

In more preferred compounds of the general formula (C4)

R ^{1 is} H, CC ₄ -alkyl, hydroxy-C ₂ -C ₄ -alkyl,

R ^{2 is} H, C ₁ -C ₃₀ -alkyl, hydroxy-C ₂ -C ₄ -alkyl, benzyl, C ₄ -C ₃₀ -alkenyl, phenyl or C ₁ -C ₄ -alkylene-OCOR ⁵ , where R ^{5 is} C ₈ -C ₈ - Alkyl or C ₈ -C ₁₈ alkenyl, R ^{3 is} H, C 1 -C ₃₀ -alkyl, C ₄ -C ₃₀ -alkenyl, benzyl, phenyl or C ₄ -alkylene-OCOR ⁵ , wherein R ^{5 is} C ₈ -C ₈ -alkyl or C ₈ -C ₈ -alkenyl,

R ^{4 is} C ₄ -C ₃₀ -alkyl, C ₄ -C ₃₀ -alkenyl, benzyl or phenyl, with the above

defined proviso.

In particularly preferred compounds of the general formula (C4), R ^{1 is} H, C ¹ -C 6 -alkyl, hydroxyethyl,

R ^{2 is} H, dC ₂ o-alkyl, hydroxyethyl, benzyl, phenyl or CH ₂ -OCOR ⁵ , where R ^{5 is} C ₈ -C ₈ -alkyl or C ₈ -C ₈ -alkenyl,

R ^{3 is} H, C ₁ -C ₂₀ -alkyl, C ₆ -C ₂ o-alkenyl, benzyl, phenyl or CH ₂ -OCOR ⁵ , wherein R ⁵

C ₈ -C ₈ -alkyl or C ₈ -C ₈ -alkenyl,

R ^{4 is} C ₆ -C ₂ o-alkyl, C6-C ₂₀ alkenyl, benzyl or phenyl, with the above

defined proviso. Examples of ammonium cations of the formula (C4) are

Stearylammonium, Oleylammonium, ethylhexylammonium, Cocosfettammonium, 3-lsotridecylether-propylammonium, Didecylammonium, Diisotridecylammonium, Dimethyldecylammonium, Jeffamine ^® M600 ammonium, triethylammonium, didecyldimethylammonium, distearyl dimethyl ammonium,

Trioctylmethylammonium, cocoalkyldimethylbenzylammonium, bis (N, N-hydroxyethyl) -dodecylmethylammonium, methyltrioctylammonium, N, N-bis-stearoylethyl-N, N-dimethylammonium. The benzotriazolium cations preferably have the general formula (C5):

wherein

R ¹ and R ^{2 are the} same or different and Ci-C- | _2- alkyl, hydroxy

(C ₁ -C ₄ alkyl, - (CC ₆ -alkylene-O-) _m -R, or C ₆ -C ₀ aryl, wherein

R is H, C 1 -C ₆ -alkyl or hydroxy-C ₁ -C ₆ -alkyl and m is a number from 1 to 20.

Preferably, R and R ^{2 are} C ₂ -C ₈ alkyl or phenyl.

The pyridinium cations preferably have the general formula (C6):

wherein

R ¹ and R ^{2 are} identical or different and C ¹ -C 6 -alkyl,

Hydroxy (C -C ₁₈ ) alkyl, - (C ₁ -C ₆ -alkylene-O-) _m -R,

in which R is H, Ci-Ci ₆ -alkyl or hydroxy-Ci-C ₁₆ -alkyl and m is a number from 1 to 20, or C ₆ -Cio-aryl, preferably

C ₄ -C 12 -alkyl or phenyl. The invention also relates to a process for preparing the compounds of the formula (I) according to the invention by diazotization of amines of the formula (A), preferably at a temperature of 0 to 10 ° C, and azo coupling with one equivalent of the pyridone coupling component of the formula (P ), preferably at a temperature of 0 to 40 ° C,

wherein

R ° to R ^{5 have} the meanings given above, and

Ex a leaving group, z. H or carbamoyl,

and, if appropriate, subsequent replacement of the cation obtained in the synthesis, for example H ⁺ or Na 1+, against the cation M ⁺ .

The compounds of the formulas (A) and (P) are known to the person skilled in the art from the literature.

In the diazotization, the amine in question is advantageously cooled to 0 to 10 ° C, preferably to 0 to 5 ° C and by adding nitrosylsulfuric acid or sodium nitrite in an acidic medium, eg. B. between pH 0 and 5, diazotized.

Subsequently, the diazotized amine is allowed to react with the coupling component P, preferably in aqueous solution. In general, the

Coupling reaction carried out at temperatures from 0 to 40 ° C. The pH is usually between 4 and 9. It can also be adjusted to the desired range by using a suitable buffer.

The resulting dyes can be removed from the reaction medium

Salination with an alkali metal salt, filtration and drying are isolated, if necessary under reduced pressure and at elevated temperature.

Depending on the reaction and work-up conditions, the dyes of formula (I) can be obtained as a free acid, as a salt or as a mixed salt containing, for example, one or more cations from the

Alkali metal cations, for example sodium ion, or the ammonium ions or phosphonium ions. If desired, the dye salts of formula (I) may be further purified, for example by diafiltration through a semipermeable membrane or recrystallization, thereby avoiding undesirable

By-products and inorganic salts are separated from the crude product.

From the Farbstoffalkalimetallsalzen the salts with the organic counterions M ^{+ can} be obtained for example by reacting an aqueous solution of Farbstoffalkalimetallsalzes at elevated temperature, for. B. 40 to 95 ° C, mixed with an aqueous solution of the counterion halide salt and the newly formed dye salt in a preferably non- or slightly water-soluble organic solvent such. As methoxypropyl acetate, extracted. From the organic phase, the dye salts of the formula (I) with the organic counterions M ⁺ after removal of the solvent, if necessary in conjunction with a

Purification step, isolate.

The compounds of the formulas (C1) to (C6) are the

Skilled in the art. Thus, for example, imidazolium halides (C1) which are used as ionic liquids as well as phase transfer catalysts can be prepared according to US 5,132,423.

Benzotriazolium halides (C5) may e.g. As described by Kuhn et al., Chem. Ber. 1940, 1109-1113. Pyridinium halides (C6) may be known to one skilled in the art

Procedure from pyridine and chloroacetic acid methyl ester as well

subsequent reaction with the corresponding amine can be obtained.

The compounds of the formula (I) according to the invention can be used for coloring high molecular weight organic materials of natural or synthetic origin, for example plastics, resins, lacquers,

in particular metallic paints, paints, electrophotographic toners and developers, electret materials, as well as inks, inkjet inks, printing inks and seeds.

High molecular weight organic materials with the inventive

Compounds can be colored, for example

Cellulose compounds, such as cellulose ethers and esters, such as

Ethylcellulose, nitrocellulose, cellulose acetates or cellulose butyrates, natural binders such as fatty acids, fatty oils, resins and theirs

Conversion products, or synthetic resins, such as polycondensates, polyadducts, polymers and copolymers, such as aminoplasts, in particular urea and melamine-formaldehyde resins, alkyd resins, acrylic resins, phenolic resins and phenolic resins, such as novolaks or resols, urea resins, polyvinyls, such as polyvinyl alcohols, polyvinyl acetals, polyvinyl acetates or polyvinyl ethers,

Polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene or polypropylene, styrene-butadiene copolymers, poly (meth) acrylates and their

Copolymers, such as polyacrylic acid esters, styrene acrylates, or polyacrylonitriles, polyamides, polyesters, polyurethanes, polysulfones, coumarone indene and

Hydrocarbon resins, Epoxy resins, Phenolic epoxy resins, Unsaturated

Synthetic resins (polyesters, acrylates) with the different hardening mechanisms, waxes, aldehyde and ketone resins, rubber, rubber and its derivatives and latices, casein, silicones and silicone resins; individually or in mixtures. It does not matter if the mentioned high molecular weight organic

Compounds as plastic masses, melts or in the form of

Spinning solutions, dispersions, paints, paints or printing inks are present. The invention likewise provides a high molecular weight organic medium containing a dyeing effective amount of a compound of the formula (I) according to the invention.

Based on the high molecular weight organic material to be colored, the compounds according to the invention are usually used in an amount of from 0.01 to 45% by weight, preferably from 0.1 to 40% by weight. Preference is given to the use of compounds of the formula (I) for color filters and the mass coloration of polymers.

Particularly preferably, the use as colorant for color filters is suitable for both additive and subtractive color production, such as

For example, in electro-optical systems such as LCD (liquid crystal displays),

OLED displays, charge coupled devices, plasma displays or electroluminescent displays, which in turn may be active (twisted nematic) or passive (supertwisted nematic) ferroelectric displays or light-emitting diodes, as well as colorants for electronic inks ("electronic inks"). "E-inks") or "electronic paper" ("e-paper").

Due to their solubility, the colorants of the formula (I) need not be subjected to dispersion in suitable solvents. It is thus possible to dissolve them in appropriate solvents mentioned below, and so in

To introduce photoresists.

The compounds of the formula (I) according to the invention can also be present as a solution or as a binder-containing colorant solution (photoresist). The present invention therefore also provides a solution containing from 0.01 to 45% by weight, preferably from 1 to 20% by weight, in particular from 2 to

17% by weight of the compounds of the formula (I) according to the invention, dissolved in an organic solvent. Suitable organic solvents are, for example:

Ethyl lactate, benzyl alcohol, 1, 2,3-trichloropropane, 1, 3-butanediol,

1, 3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxyethylpropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol,

3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate,

4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, gamma-butyrolactone, isobutyl alcohol,

Isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether,

Ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-tert-butyl ether,

Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate,

Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether,

Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate,

Diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether,

Diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate,

Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate,

Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate,

Cyclohexanone, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether,

Dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether,

Diacetone alcohol, triacetylglycerol, tripropyleneglycol monobutyl ether,

Tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether,

Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate,

Propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic ester (DBE). Particularly advantageous are ethyl lactate, propylene glycol monomethyl ether acetate (methoxypropyl acetate), propylene glycol monoethyl ether acetate,

Ethylene glycol monomethyl ether acetate, ketones such as cyclohexanone or alcohols such as n-butanol or benzyl alcohol.

The organic solvents can be used alone or in mixtures with one another.

Depending on the application, the compounds according to the invention may be combined with customary auxiliaries or additives to give a colorant composition, for example surfactants, dispersants, rheology control additives, fillers, control agents, resins, waxes, defoamers, anti-dust agents, extenders, antistatic agents, charge control agents,

Preservatives, drying retardants, wetting agents, antioxidants, UV absorbers, light stabilizers, and binders, for example, the binders of the system in which the composition according to the invention is to be used. If available, the aids and additives

preferably in an amount of 0.01 to 15 wt .-%, in particular 0.5 to 10 wt .-%, based on the total weight of the colorant composition used.

In particular for color filters, the inventive

Colorant composition, for example, still contain surfactants, dispersants, resins and waxes. The invention likewise provides a binder-containing colorant solution containing 0.01 to 40% by weight, preferably 0.1 to 30% by weight, in particular 1 to 20% by weight, of the colorant of the formula (I) according to the invention in at least one organic solvent, at least one polymeric binder and optionally further auxiliaries.

The binder-containing colorant solution is conveniently prepared by mixing the colorant solution described above with the other components mentioned. As polymeric binders are, for example, acrylates, acrylic esters, polyimides, polyvinyl alcohols, epoxies, polyesters, melamines, gelatin, caseins and

polymerizable ethylenically unsaturated monomers and oligomers, preferably those which crosslink either thermally or under the influence of UV light and radical initiators. The polymeric binders are useful in an amount of 5 to 90 wt .-%, preferably from 20 to 70 wt .-%, based on the total amount of all non-volatile constituents of the colorant solution. Non-volatile constituents are understood as meaning the compounds of the formula (I), the polymeric binders and the other auxiliaries.

By volatile components is meant the organic solvents which are volatile under the applied baking temperatures.

Crosslinking agents and radical initiators, leveling agents, defoamers and deaerators may be considered as further auxiliaries. They are useful in an amount of 0 to 10 wt .-%, preferably from 0 to 5 wt .-%, based on the total amount of the colorant solution.

In the case that other auxiliaries are used, a lower limit of 0.01 wt .-%, preferably 0.1 wt .-%, is appropriate, based on the

Total amount of colorant solution.

The yellow shades of the compounds of the invention and

Colorant compositions are particularly well suited to the Color Filter Red-Green-Blue (R, G, B) color set. These three colors are present as separate color points next to each other, and result from backlit one

Full color image. In addition, there are color filter systems that work with four primary colors red-green-blue and yellow (R, G, B, Y), for which the colorants of the invention are also well suited.

The invention further provides the use of the above

described colorant of formula (I), as well as in the form of the described solution or binder-containing colorant solution in color filters. The use concentration of the colorants according to the invention in the applied color filter film can be between 5 and 95% by weight, preferably between 10 and 70% by weight, very particularly preferably between 15 and 50% by weight, based on the total weight of the Color filter film.

The invention also provides a color filter comprising a dyeing effective amount of the colorants of the invention. In the following examples, percentages are percentages by weight and parts by weight unless otherwise stated.

Examples:

Preparation of the acid azo dye (I a):

A suspension consisting of 17.1 g of 4-amino-phenyl-methylsulfone (0.10 mol) in 100 ml of water and 22 ml of conc. Hydrochloric acid (37% strength by weight) is diazotized at 0 ° -5 ° C. with 17.3 g sodium nitrite solution (40% strength by weight, 0.1 mole NaNO ₃ ). The resulting diazonium salt is added in portions at 0 to 5 ° C to a suspension consisting of 24.6 g (0.1 mol) of the compound of the following formula

in 9 ml of 30% sodium hydroxide solution and 50 ml of water. By adding

15 wt .-% sodium carbonate solution, the pH is maintained at 7 to 9. The volume of the dye suspension is made up with water to about 700 ml, then heated to 90 ° C for 30 min. After cooling, the product is filtered off with suction, washed with water and dried in vacuo. 40.2 g of a yellow dye powder of the formula (Ia) are obtained.

Preparation of hexaalkylguanidinium chloride (C2a):

To a solution of 15.5 ml (0.13 mol) of tetramethylurea in 60 ml of toluene 13 ml (0.13 mol) of phosphoryl chloride are added dropwise at 60 - 65 ° C. After two hours of stirring is cooled and added dropwise at 0 - 5 ° C, a mixture of 18 ml of triethylamine and 40 ml (0.14 mol) of bis (2-ethylhexyl) amine in 30 ml of toluene. Subsequently, the temperature is allowed to rise to about 20 ° C and stirred overnight. Then, the pale yellow mixture is added with cooling with 54 ml of NaOH (30 wt .-%). The mixture is stirred with 150 ml of NaCl solution. The toluene phase is separated off, dried with magnesium sulfate and the solvent is removed in vacuo. This gives 47 g of a light beige,

waxy solid. Preparation of hexaalkylguanidinium dye salt (I b):

27.5 g (66 mmol) of Hexaalkylguanidiniumchlorids (C2a) are dissolved at 90 ° C in 500 ml of water with stirring (solution A).

29.2 g (64 mmol) of the yellow acid azo dye of the formula (I a) are introduced into 500 ml of water and heated to 60 to 65 ° C after the addition of five drops of 15 wt .-% sodium carbonate solution. This suspension is added in portions at about 90 ° C to solution A. After one hour reaction time at this temperature, an emulsion is obtained from which after cooling the

Water phase is decanted off. The oily organic phase is taken up in 350 ml of methoxypropyl acetate, dried with magnesium sulfate and stored at 4 ° C. for one night. After filtering off the precipitated solid, the solvent is removed in vacuo and the residue obtained is dried to constant weight.

By analogous procedure, the dyes were obtained in Table 1.

For the dye anion of Example II, an equivalent amount of 4-aminophenyl p-tolylsulfone is used instead of 4-aminophenyl methylsulfone. For the dye anions of examples I m to 1 p, instead of 4-aminophenyl methylsulfone, an equivalent amount of 4-aminophenylsulfonic acid is used. Table 1 (prepared dye salts)

These are yellow substances with decomposition points> 200 ° C. Further dye anions were prepared starting from the following nitrilopyridones:

They are made of methyl cyanoacetate, methyl acetoacetate and the corresponding amine-methoxypropylamine or Jeffamine ^® M600 - accessible. The nitrile group can be removed by heating with dilute sulfuric acid. The 3.5 unsubstituted pyridones obtained are reacted with formaldehyde and sodium bisulfite according to a known procedure (analogous to DE 2162858), the following pyridone couplers being obtained.

R = methyl. From this, the dyes I q and I s were obtained. The reaction of the named Na dye salts with the respective quaternary ammonium compounds analogously to the preparation of I b gave the dye salts I r and 1 1.

Application Testing Colorfilter:

Application example A1:

1.00 g of the compound (I b) are added to 22.9 g of 1-methoxy-2-propyl acetate. Is added 0.33 g of n-butanol, 0.65 g Disperbyk ^® 2001 (BYK-Chemie GmbH, a modified acrylate block copolymer in solution

Methoxypropyl / butyl glycol / methoxypropanol 2/2/1) and 10.8 g Ripoxy ^® SPC 2000 (Showa High Polymer Co., Ltd., acrylate polymer solution

Methoxypropyl acetate) and stirred for 2 hours at room temperature. The obtained

Mixture is filtered.

The obtained binder-containing colorant solution is applied with the aid of a spin coater (POLOS Wafer Spinner) on glass plates (SCHOTT, laser-cut, 10 × 10 cm) in a layer thickness which, when using a light source C, the color coordinates y mentioned in Table 2 as Set reference values.

The layer thickness is in each case about 1 to 2 micrometers.

The glass plates are allowed to flash off and then dried for 10 min at 80 ° C. in a circulating air drying cabinet (Binder). Of the glass plates, the so-called prebake values of the color coordinates (x, y, Y, as well as CIELAB, spectrophotometer Datacolor 650, illuminant C, 2 ° observer),

Measure transmission curves (ditto) and contrast values (Contrast Tester Tsubosaka CT-1; blank 5000). The glass plates are then one Heat treatment at 230 ° C for 1 h in a convection oven and re-measured, from which one receives the postbake values.

Application examples A2 - A10

The solutions are prepared analogously as in the case of Application Example A1. However, instead of compound I b, the compounds mentioned in table 2 are used.

Table 2 shows the results of the examples according to the invention in the postbake. The values x, y and Y denote the measured color coordinates in the CIE-Yxy standard color space, where Y is a measure of the brightness.

Table 2: (reference to y-values).

The coated glass plates (color filter) of the invention

Compositions each have transparent, greenish-yellow colorations. The colorations in each case show high contrast values and brightness values Y. Likewise, they exhibit steep transmission curves.

Claims

claims:

1. Compounds of the formula (I)

wherein

R ° C ₁ -C ₆ -alkyl or CF ₃ ;

R ¹ sulfo, carboxy, C 1 -C ₄ -alkylene-carboxy, CONH ₂ ,

CONH (CC ₄ -alkyl) or CN,

R ² Ci-Ci ₈ alkyl, C ₂ -C ₁₈ alkenyl, hydroxy-Ci-C ₁₈ alkyl, or - (CrC ₆ -alkylene-O-) _m -R, wherein R is H, Ci-Ci Has _6- alkyl or hydroxy-Ci-Ci ₆ -alkyl and m is a number from 1 to 20,

R ^{J is} H, sulfo, carboxy, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy,

R ^{4 is} H, CC ₆ -alkyl or C 1 -C ₆ -alkoxy,

R ^{5 is} OH, OM, Ci-Ce-alkyl, unsubstituted C ₆ -C ₁₀ aryl or substituted by Ci-C ₆ alkyl, halogen, carboxyl or sulfo C ₆ -Cio-aryl

in which the compounds of the formula (I) contain at least one anionic radical from the group consisting of sulfo and carboxy with the counter cation M ⁺ , where M ⁺ denotes an alkali metal cation or an organic cation.

2. Compounds according to claim 1, characterized in that the

Compounds of formula (I) contain at least one sulfo group with the counter cation M ⁺ .

3. Compounds according to claim 1 or 2, characterized in that the counter cation IvT is an organic cation from the group of Imidazoliumkationen, Alkylguanidiniumkationen, phosphonium, primary, secondary, tertiary or quaternary ammonium cations, benzotriazolyl cations and

Pyridiniumkationen is.

4. Compounds according to one or more of claims 1 to 3, characterized in that

R ° is CC ₂ alkyl.

5. Compounds according to one or more of claims 1 to 4, characterized in that

R ¹ (dC ₂ alkylene) sulfo, CONH (Ci-C ₂ alkyl) or CONH ₂ means.

6. Compounds according to one or more of claims 1 to 5, characterized in that

R ^{2 is} C 1 -C ₈ -alkyl, hydroxy-C 1 -C 5 -alkyl or - (C 1 -C ₄ -alkylene-O-) _m -R, where R is H or C 1 -C 10 -alkyl and

m is a number from 1 to 15 is.

7. Compounds according to one or more of claims 1 to 6, characterized in that

R ^{3 is} H, a sulfo group, C 1 -C ₄ -alkyl or C 1 -C ₄ -alkoxy.

8. Compounds according to one or more of claims 1 to 7, characterized in that

R ^{4 is} H, Ci-C alkyl or CC alkoxy.

9. Compounds according to one or more of claims 1 to 8, characterized in that

R ⁵ OH, O ^" M ⁺ , d-OrAlkyl, one with CC ₂ alkyl, halogen or sulfo

substituted phenyl or unsubstituted phenyl, wherein M ^{+ is} an alkali metal cation, a quaternary ammonium cation or a

Phosphonium cation means.

10. Compounds according to one or more of claims 1 to 9, characterized in that

R ° methyl,

R ^{1 is} CH ₂ -sulfo or CONH ₂ ,

R ^{2 is} ethyl or - (C ₂ -C ₃ -alkylene-O-) _m -R, where

R is H or methyl and

m is a number from 1 to 12,

R ^{3 is} H or methyl,

R ⁴ H,

R ^{5 is} OH, ΟΊνΓ, methyl, tolyl or phenyl,

wherein the compounds of formula (I) contain 1 or 2 sulfo groups and the counter cation M ^{+ represents} an alkali metal cation, an organic ammonium cation or an organic phosphonium cation.

11. A process for the preparation of the compounds according to at least one of claims 1 to 10 by diazotization of amines of the formula (A) and

Azocoupling with one equivalent of the pyridone coupling component of the formula (P),

wherein

R ° to R ⁵ are defined as in claim 1 and

Ex represents a leaving group

and optionally subsequent cation exchange with introduction of the cation M ⁺ .

12. A solution containing 0.01 to 45 wt .-% of one or more compounds of formula (I) according to one or more of claims 1 to 10, dissolved in an organic solvent.

13. Binder-containing colorant solution containing 0.01 to 40 wt .-% of one or more compounds of the formula (I) according to one or more of claims 1 to 10, dissolved in at least one organic solvent, at least one polymeric binder and optionally further auxiliaries.

14. Use of compounds of the formula (I) according to one or more of claims 1 to 10 for coloring high molecular weight organic materials of natural or synthetic origin

15. Use according to claim 14 for dyeing for color filters, in

Liquid crystal displays or in OLED displays or for Polymermassefärbung.