DE102007050193A1 - Finely divided C.I. Pigment Yellow 155 - Google Patents

Abstract

The present invention relates to a novel finely divided C.I. Pigment Yellow 155 of the formula (I), $ F1 characterized by a mean particle size d50 of 20 to 50 mm and d95 of 40 to 100 and the signals characteristic of the beta phase in the X-ray powder diffractogram.

Description

The The present invention relates to a novel, finely divided and lightfast C.I. Pigment Yellow 155.

to Production of highly transparent permanent dyeings particularly finely divided organic color pigments needed, to largely exclude particle scattering. Across from likewise highly transparent dye stains have pigments a much better lightfastness. The combination of transparency with lightfastness is especially in the fields of decor printing, ink-jet printing and color filters of great interest.

in Form der Beta-Kristallphase allein oder in Kombination mit anderen Farbmitteln eingesetzt, da es einen reinen Farbton mit hoher Transparenz und mit einer sehr guten Lichtechtheit verbindet.For greenish yellows is increasingly CI Pigment Yellow 155 of the formula (I)

used in the form of the beta crystal phase alone or in combination with other colorants, since it combines a pure hue with high transparency and with a very good light fastness.

The beta phase of CI Pigment Yellow 155 is characterized by the following lines in the X-ray powder diagram (Cu-K _α1 radiation, double diffraction angles 2Θ in degrees, lattice spacings d in Å ^-1 ): 2Θ d rel. intensity 5.51 16.0 21 10.04 8.8 77 11.16 7.9 22 16.74 5.3 18 17.66 5.0 13 19.32 4.6 20 21.82 4.1 15 25.07 3.5 6 26.88 3.3 100 29,01 3.1 6 30.37 2.9 6 32.86 2.7 4

The beta phase is obtained, for example, by treatment with solvents, as described, for example, in US Pat DE 40 39 590 A1 by treatment with dimethylformamide or in US 4,003,886 by treatment with dichlorobenzene.

In addition to the beta form of CI Pigment Yellow 155, the alpha phase has also become commercially important for the coloring of plastics as indicated by the following lines in the X-ray powder diagram (Cu-K _α1 radiation, double diffraction angles 20 degrees, lattice spacings d in Å ^-1 ) is characterized: 2Θ d rel. intensity 8.35 10.6 41 9.95 8.9 71 16.60 5.3 31 20.52 4.3 36 26.79 3.3 100

The alpha phase is usually obtained directly after the aqueous coupling, as described, for example, in US Pat US 3,997,521 Example 20 and in DE 2,058,849 Example 55. A very broad particle size distribution is always obtained which renders these products unusable for printing applications.

by virtue of the redder hue has the alpha phase opposite the beta phase has not gained any technical importance in printing applications. In addition, the beta phase has a higher light fastness as the alpha phase.

WO 2006/093940 describes salt kneading and ball milling of coarse CI Pigment Yellow 155 to give a material having a specific surface area greater than 40 m ² / g. About the crystal phase of the starting material and the final product, the font makes no statement.

The beta phase of CI Pigment Yellow 155 is always present in coarse-particle form according to the previously known processes. Solvent treatment or comminution of coarse-grained CI Pigment Yellow 155 by conventional methods of fine dispersion gives pigments of average particle size d ₅₀ greater than 60 nm and d 95 greater than 130 nm. See 1 ,

The beta phase of CI Pigment Yellow 155 in its previously known form is associated with disadvantages. Due to the average particle size d ₅₀ of greater than 60 nm, the processing properties, especially in ink-jet printing through the use of very fine nozzles are not always satisfactory. Also, the beta phase of CI Pigment Yellow 155 in its previously known form due to a significant proportion of particles in the scattering range does not have the transparency required in some applications. The color strength of the known beta phase of CI Pigment Yellow 155 is not always sufficient.

It Thus, the task was as greenish as possible C.I. Pigment Yellow 155 in a very finely divided crystal form provide without significantly affecting the light fastness.

It has been found that a CI Pigment Yellow 155 in the beta phase with an average particle size distribution d ₅₀ of 20 to 50 nm and a d ₉₅ of 40 to 100 nm surprisingly achieves this object.

in der beta-Kristallphase,
gekennzeichnet durch eine mittleren Teilchengrößenverteilung d₅₀ von 20 bis 50 nm und einem d₉₅ von 40 bis 100 nm, vorzugsweise d₅₀ 25 bis 45 nm und d₉₅ von 50 bis 90 nm.The invention relates to a CI Pigment Yellow 155 of the formula (I)

in the beta crystal phase,
characterized by an average particle size distribution d ₅₀ of 20 to 50 nm and a d ₉₅ of 40 to 100 nm, preferably d ₅₀ 25 to 45 nm and d ₉₅ from 50 to 90 nm.

Surprisingly, dyeings of a CI Pigment Yellow 155 according to the invention show no significant drop in light fastness compared to the known beta-form according to US 4,003,886 (eight-level blue scale, check after DIN 12040 ).

It has been found that, surprisingly, only a salt kneading of CI Pigment Yellow 155, which already has a BET specific surface area of greater than or equal to 70 m ² / g, with inorganic salts in the presence of an organic solvent leads to the pigments according to the invention. It is furthermore surprising that the starting material can be used both in the alpha phase and in the beta phase or in a mixture of the two phases.

If a CI Pigment Yellow 155 with a specific surface area of less than 40 m ² / g is used as the starting material, only products with particle size d ₅₀ of more than 60 nm are obtained even with longer kneading times. By other grinding methods, such as. As dry grinding and milling in suspension, pigments are obtained which have a considerable proportion of coarser crystals with a particle size d ₉₅ of at least 100 nm.

The invention therefore also provides a process for the preparation of the inventive CI Pigment Yellow 155, characterized by the kneading of an alpha and / or beta crystal phase of CI Pigment Yellow 155, which has a specific surface area of greater than or equal to 70 m ² / g with a crystalline inorganic salt in the presence of an organic solvent.

When inorganic salt are preferably alkali or alkaline earth halides, Alkali or alkaline earth carbonates, alkali or alkaline earth sulfates, Aluminum sulfate or a combination thereof used. Especially preferred are sodium or potassium halides. Very particularly preferred are Sodium or potassium chloride. Preferably, the kneading is at 30 to 150 ° C for 0.1 to 100 h. Particularly preferred is a kneading at 60 to 130 ° C for 1 to 48 h.

The Ratio of inorganic salt to C.I. Pigment Yellow 155 can be varied widely. Preferred is a Pigment-salt ratio of 1: 0.5 to 1:50, preferably 1: 1 to 1:20, more preferably 1: 2 to 1:10. The weight ratio between the organic solvent and the inorganic salt is preferably 1 ml: 10 g to 1 ml: 1 g. The weight ratio between the organic solvent and the sum of inorganic Salt and pigment is preferably 1 ml: 10 g to 1 ml: 2 G.

The organic solvent may be miscible or immiscible with water. Suitable organic solvents are alcohols having 1 to 10 C atoms, such as, for example, methanol, ethanol, n-propanol, isopropanol, butanols, such as n-butanol, isobutanol, tert-butanol, pentanols, such as n-pentanol, Methyl-2-butanol, hexanols, such as 2-methyl-2-pentanol, 3-methyl-3-pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol, octanol, such as 2,4,4- Trimethyl-2-pentanol, cyclohexanol; or glycols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, or glycerol; Polyglycols, such as polyethylene or polypropylene glycols; Ethers, such as methyl isobutyl ether, tetrahydrofuran, dimethoxyethane or dioxane; Glycol ethers, such as monomethyl or monoethyl ethers of ethylene or propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl glycols or methoxybutanol; Ketones, such as acetone, diethyl ketone, methyl isobutyl ketone, methyl ethyl ketone or cyclohexanone; aliphatic acid amides such as formamide, dimethylformamide, N-methylacetamide or N, N-dimethylacetamide; Urea derivatives, such as tetramethylurea; or cyclic carboxylic acid amides, such as N-methylpyrrolidone, valero or caprolactam; Esters, such as carboxylic acid C ₁ -C ₆ -alkyl esters, such as butyl formate, ethyl acetate or propionic acid propyl ester; or carboxylic acid C ₁ -C ₆ glycol ester; or glycol ether acetates such as 1-methoxy-2-propyl acetate; or phthalic or benzoic acid C ₁ -C ₆ alkyl esters, such as ethyl benzoate; cyclic esters such as caprolactone; Nitriles, such as acetonitrile or benzonitrile; aliphatic or aromatic hydrocarbons, such as cyclohexane or benzene; or benzene substituted by alkyl, alkoxy, nitro or halogen, such as toluene, xylenes, ethylbenzene, anisole, nitrobenzene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene or bromobenzene; or other substituted aromatics such as benzoic acid or phenol; aromatic heterocycles such as morpholine, picoline or quinoline; and hexamethylphosphoric triamide, 1,3-dimetyl-2-imidazolidinone, dimethylsulfoxide and sulfolane.

Especially preferred are glycols.

at The choice of solvents should be taken care of are stable under the chosen conditions.

To Completing the salt kneading are the inorganic salts in water dissolved, optionally in the presence of an acid or lye. The pigment is purified by filtration in the usual way isolated. Before isolation of the pigment, the solvent by distillation, optionally under reduced pressure, or by Steam distillation can be removed.

The finely divided CI Pigment Yellow 155 isolated after kneading may, after filtration as a filter cake or as a dried material, optionally be subjected to a solvent aftertreatment in order to obtain a more homogeneous particle shape without appreciably increasing the particle size. Preferably, the use of water or steam-volatile solvents such as alcohols and aromatic solvents, more preferably branched or unbranched C ₁ -C ₆ alcohols, toluene, xylene, chlorobenzene, dichlorobenzene, nitrotoluene or nitrobenzene usually at elevated temperature, for example up to 200 ° C, and optionally under elevated pressure.

at The drying of a wet pigment, the known Drying units are used, such as drying cabinets, Paddle wheel dryers, tumble dryers, contact dryers and in particular spinflash and spray dryer.

The pigment according to the invention can be further customary Auxiliaries and additives are provided, such as Surfactants, non-pigmentary or pigmentary dispersants, Fillers, extenders, resins, waxes, defoamers, Anti-dust agents, extenders, antistatic agents, preservatives, antioxidants, drying retardants, Wetting agents, UV absorbers and light stabilizers, preferably in from 0.1 to 30% by weight, in particular from 0.5 to 10% by weight, based on the total weight of the pigment and the said aids and additives.

When Surfactants are anionic or anionic, cationic or cationic and nonionic or amphoteric substances or mixtures thereof Means into consideration.

When anionic substances are, for example, fatty acid taurides, Fatty acid N-methyltauride, fatty acid isethionate, Alkylphenylsulfonates, for example dodecylbenzenesulfonic acid, Alkylnaphthalenesulfonates, alkylphenol polyglycol ether sulfates, fatty alcohol polyglycol ether sulfates, Fatty acid amide polyglycol ether sulfates, alkyl sulfosuccinamates, alkenyl succinic acid half esters, Fatty alcohol polyglycol ether sulfosuccinates, alkanesulfonates, fatty acid glutamates, Alkyl sulfosuccinates, fatty acid sarcosides; fatty acids, for example, palmitic, stearic and oleic acid; the salts of these anionic substances and soaps, for example Alkali metal salts of fatty acids, naphthenic acids and Resin acids, for example abietic acid, alkali-soluble Resins, for example rosin-modified maleate resins and Condensation products based on cyanuric chloride, taurine, N, N'-diethylaminopropylamine and p-phenylenediamine into consideration. Preferred are rosin soaps, d. H. Alkali salts of resin acids.

When Cationic substances come, for example, quaternary Ammonium salts, Fettaminoxalkylate, polyoxyalkyleneamines, alkoxylated Polyamines, fatty amine polyglycol ethers, primary, secondary or tertiary amines, for example alkyl, cycloalkyl or cyclized alkylamines, in particular fatty amines, of fatty amines or Fatty alcohols derived di- and polyamines and their oxalkylates, derived from fatty acids imidazolines, polyaminoamido or polyamino compounds or resins having an amine index between 100 and 800 mg KOH per g of the polyaminoamido or polyamino compound, and salts of these cationic substances, such as Acetates or chlorides, into consideration.

When Nonionic and amphoteric substances are, for example, fatty amine carboxyglycinates, amine oxides, Fatty alcohol polyglycol ethers, fatty acid polyglycol esters, betaines, such as fatty acid amide N-propyl betaines, phosphoric acid esters of aliphatic and aromatic alcohols, fatty alcohols or Fatty alcohol polyglycol ethers, fatty acid amide ethoxylates, fatty alcohol alkylene oxide adducts and alkylphenol polyglycol ethers.

The C.I. Pigment Yellow 155 according to the invention alone or in mixtures containing the inventive Pigment, for pigmenting high molecular weight organic Materials of natural or synthetic origin, eg. As paints, plastics, resins, paints, printing inks, Pigment preparations, in particular aqueous or solvent-based pigment preparations, electrophotographic Toners and developers, inks, ink-jet inks, color filters and electronic inks, and for coloring seeds. The invention, finely divided C.I. Pigment Yellow 155 is particularly suitable for Coloring of color filters, printing inks for decorative prints and ink-jet inks, as well as all highly transparent paints and films for electronic applications.

Under electrophotographic toners and developers become on or off Two-component powder toners (also one- or two-component developers magnetic toner, liquid toner, latex toner, polymerization toner and special toners, which are well known to those skilled in the art are.

Under Inkjet inks are those based on aqueous or non-aqueous Base, microemulsion inks as well as inks that use the hot-melt process work, understood, which are well known in the art. Ink-jet inks in the context of the present invention generally included in total From 0.5 to 15% by weight, preferably from 1.5 to 8% by weight, calculated as dry of the pigment according to the invention.

Microemulsion inks based on organic solvents, water and possibly one additional hydrotropic substance (interface mediator). Microemulsion inks generally contain from 0.5 to 15% by weight, preferably 1.5 to 8 wt .-%, of the inventive Pigments, 5 to 99 wt .-% water and 0.5 to 94.5 wt .-% organic Solvent and / or hydrotrope. "Solvent based ink-jet inks preferably contain 0.5 to 15 wt .-% of pigment according to the invention, 85 to 99.5% by weight organic solvent and / or hydrotrope compounds.

Hot-melt inks are mostly based on waxes, fatty acids, fatty alcohols or Sulfonamides, which are solid at room temperature and when heated become liquid, with the preferred melting range between approx. 60 ° C and about 140 ° C. Hot melt ink jet inks exist z. B. essentially from 20 to 90 wt .-% wax and 1 to 10% by weight of the pigment according to the invention. Furthermore, 0 to 20 wt .-% of an additional Polymer (as "dye remover"), 0 to 5% by weight of dispersing assistant, 0 to 20% by weight of viscosity modifier, 0 to 20 % By weight plasticizer, 0 to 10% by weight tackiness additive, 0 to 10% by weight of transparency stabilizer (prevents, for example, crystallization the wax) and 0 to 2 wt .-% antioxidant.

In In the following examples, percentages are percentages by weight.

For the particle size distribution becomes a series of electron microscopic Recordings used. The primary particles become visual identified. The area of the primary particles becomes determined by means of a graphic tablet. Out of the plane the diameter of the area of the same circle is determined. The frequency distribution of the calculated equivalent diameter is determined, the frequencies are converted into volume fractions and shown as a particle size distribution.

example 1

75 g of CI Pigment Yellow 155 in the alpha phase, prepared analogously to Example 20 of US 3,997,521 and obtained with a BET specific surface area of greater than 70 m ² / g, are kneaded with 450 g of micronised sodium chloride and 100 ml of diethylene glycol for 4 hours at 80 ° C in a Sigma blade kneader. The kneaded mass is stirred for 2 hours at 40 ° C. in 4.5 liters of 5% strength by weight hydrochloric acid, the suspension is filtered off with suction, the presscake is washed salt-free with water and dried at 80 ° C. The granules obtained are pulverized. There are obtained 71 g of CI Pigment Yellow 155 in the beta-crystal modification with a particle size (d ₅₀ ) of 35 nm and (d ₉₅ ) of 59 nm. 2 shows the diagram of the particle size distribution.

Comparative Example 1

Analogous to WO 2006/093940 , Example 2, 75 g of CI Pigment Yellow 155, starting material prepared analogously to the example of DE 40 39 590 A1 as kneaded beta crystal modification with a specific surface area of 34 m ² / g with 450 g of micronised sodium chloride and 110 ml of diethylene glycol for 6 hours at 80 ° C in a kneader with sigma blades. The plasticine is stirred in 4.5 liters of 5 wt .-% hydrochloric acid for 2 hours at 40 ° C, the suspension is filtered off with suction, washed the presscake with salt-free water and dried at 80 ° C. The resulting granules are pulverized. There are obtained 72 g of CI Pigment Yellow 155 in the beta crystal modification with a particle size (d ₅₀ ) of 61 nm and one (d ₉₅ ) of 149 nm. 1 shows the diagram of the particle size distribution.

Example of use:

Examination of the coloristic properties of the pigment preparations in an aqueous base varnish system for Ink-jet inks:

To determine the color strength and the CIELAB values, in each case 1 part of the pigment preparation with 9 parts of an aqueous base varnish system based on ethylene glycol (about 57% ethylene glycol, about 20% water, Rest aids, such as. As defoamer) and then dispersed, with a Anreibegemisch arises. For whitening, homogenize 2 parts of this grinding mixture with 100 parts of a standard white dispersion (white dispersion color 236 / 14E, Esser) and fold onto a test card. Subsequently, the coloristic properties (color strength and rating against standard) using a spectrophotometer CM-3700d Minolta determined.

Determination of transparency:

to Determination of transparency are each 4 parts of the Anreibegemisches with 9 parts of distilled water and 7 parts of a acrylate firnisses (®Viacryl SC 175 W / 40) homogenized and mounted on a test chart. As standard for color strength and transparency the pigment from Comparative Example 1 was used.

The assessment of transparency then takes place visually:
-VI significantly more covering
-V much more opaque
-IV much more opaque
-III noticeably more opaque
-II something more opaque
-I a bit more covering
/ = / about how
+ I a track more transparent
+ II a bit more transparent
+ III noticeably more transparent
+ IV much more transparent
+ V much more transparent
+ VI significantly more transparent sample Brightness (ΔL) Purity (ΔC) Hue (ΔH) Color intensity (%) transparency default example 1 2 brighter 2 purer 2 greener 165% + V tra Comparative Example 1

The inventive pigment is characterized in comparison with the pigment obtained in Comparative Example 1 by a very high color strength, a light and green hue and above all by a higher purity and a substantial one higher transparency.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• DE 4039590 A1 [0005, 0040]
• - US 4003886 [0005, 0015]
• US 3997521 [0007, 0039]
• - DE 2058849 [0007]
• - WO 2006/093940 [0009, 0040]

Cited non-patent literature

• - DIN 12040 [0015]

Claims (9)

CI Pigment Yellow 155 of the formula (I),

in the beta crystal phase, characterized by an average particle size d ₅₀ of 20 to 50 nm and d ₉₅ of 40 to 100 nm. CI Pigment Yellow 155 according to claim 1, characterized by an average particle size d ₅₀ of 25 to 45 nm and d ₉₅ of 50 to 90 nm. A process for the preparation of CI Pigment Yellow 155 according to claim 1 or 2, characterized by the kneading of an alpha and / or beta crystal phase of CI Pigment Yellow 155, which has a specific surface area of greater than or equal to 70 m ² / g, with a crystalline inorganic salt in the presence of an organic solvent. Method according to claim 3, characterized that the crystalline inorganic salt is an alkali or alkaline earth halide, an alkali or alkaline earth carbonate, an alkali or alkaline earth sulphate, Aluminum sulfate or a combination thereof. Method according to claim 3 or 4, characterized that the organic solvent is a glycol. Method according to one or more of the claims 3 to 5, characterized in that after kneading a solvent treatment in water or steam-volatile solvents is carried out. Use of C.I. Pigment Yellow 155 according to claim 1 or 2 for pigmenting high molecular weight organic materials of natural or synthetic origin. Use according to claim 7 for pigmenting inks, Printing inks, electrophotographic toners and developers, and of films for electronic applications. Use according to claim 8 for pigmenting color filters and ink-jet inks.