DE102008009194A1 - Pigment preparation, useful to pigment e.g. preferably plastics, resins, lacquers and inkjet-inks, comprises C.I. Pigment Blue with a specific average particle size and a nitro-sulfoxide compound, as a pigment dispersant - Google Patents

Abstract

Pigment preparations (I) comprise C.I. Pigment Blue 15:6 with an average particle size of 10-100 nm and at least a nitro-sulfoxide compound (II), as a pigment dispersant. Pigment preparations (I) comprise C.I. Pigment Blue 15:6 with an average particle size of 10-100 nm and at least a nitro-sulfoxide compound of formula (CPC-(S(=O) 2(O ->)) n(N +>(R 1>)(R 2>)(R 3>)(R 4>)) m(cation) o) (II), as a pigment dispersant. CPC : copper phthalocyanine; n, m : 0.1-4, preferably 0.2-2; cation : a cation from the group of alkali metals, preferably Li +>, Na +>or K +>, or H +>; o : 0-3.9, preferably 0-1.8; and R 1>-R 4>a residue from the group comprising 1-20C-alkyl, 2-20C-alkenyl, 5-20C-cycloalkyl, 5-20C-cycloalkenyl, 1-4C-alkylphenyl (all optionally branched and optionally substituted by sulfo, carboxyl, OH or halo), preferably 6-20C-alkyl, 6-20C-alkenyl or benzyl or H. Provided that: 1-3 residues of R 1>-R 3>is H; and n is a sum of m and o. An independent claim is included for the preparation of (I) comprising reacting C.I. Pigment Blue 15:6 with (II) before preserving or after kneading, wet grinding, dry grinding or finish treating process.

Description

The The present invention relates to novel finely divided pigment preparations with C.I. Pigment Blue 15: 6 as the base pigment and certain pigment dispersants and their use in particular for color filters.

Copper phthalocyanine pigments For color filter applications often have a very high viscosity and poor viscosity stability. Also, the finely divided pigments are prone to agglomerate and aggregate, which is particularly detrimental to transparency, color strength and especially the contrast ratio of these pigments produced color filters.

For the measurement of the contrast ratio (KV) becomes the light intensity after irradiating a pigmented lacquer layer on a transparent Substrate determines where the substrate is between two polarizers located. The contrast ratio gives the ratio the light intensities in parallel and perpendicular Polarizers on.

EP-A 0 638 615 describes the salt kneading of crude copper phthalocyanines in the presence of copper phthalocyanine sulphonic acid ammonium salts for use in printing inks. A disadvantage of this method is the conversion of un-stabilized crude copper phthalocyanines into the undesirable beta phase in the salt kneading process.

JP 2005-234009 describes pigment preparations which, in addition to epsilon-copper phthalocyanines, contain sulfonamides, phthalimidomethyl derivatives and sulfonic acids of copper phthalocyanines. Here, the use of several synergists adversely affects the hue of the epsilon-copper phthalocyanine pigment preparation, since the synergists generally have a more greenish hue than the epsilon-copper phthalocyanine.

WO 02/48268 and WO 02/48269 describe pigment preparations of organic pigments and sulfonic acid-containing pigment dispersants, which are laked with Ca ions and / or quaternary ammonium ions. However, the preparations described do not meet the necessary high standards of contrast ratio and brilliance.

Consequently the object was to prepare pigment preparations with C.I. Pigment Blue 15: 6 as a base pigment to provide a pure color, high brilliance, low viscosity and show high contrast ratios in color filter applications.

It it was found that pigment preparations based on C.I. Blue 15: 6 and the pigment dispersants defined below Solve a task.

wobei
CPC ein Rest eines Kupferphthalocyanins,
n eine Zahl von 0,1 bis 4, vorzugsweise 0,2 bis 2,
m eine Zahl von 0,1 bis 4, vorzugsweise 0,2 bis 2,
Kat ein Kation aus der Gruppe der Alkalimetalle oder H⁺;
0 eine Zahl von 0 bis 3,9, vorzugsweise von 0 bis 1,8, wobei n = m + o gilt;
R¹, R², R³, R⁴ voneinander unabhängig jeweils Wasserstoff, oder einen Rest aus der Gruppe C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₅-C₂₀-Cycloalkyl, C₅-C₂₀-Cycloalkenyl, C₁-C₄-Alkyl-phenyl bedeuten, wobei die vorstehend genannten Reste gegebenenfalls verzweigt und gegebenenfalls durch Sulfo, Carboxy, Hydroxy und Halogen substituiert sind,
mit der Maßgabe, dass ein, zwei oder drei der Reste R¹ bis R⁴ Wasserstoff bedeuten.The invention relates to pigment preparations comprising CI Pigment Blue 15: 6 having an average particle size d _{50 of} from 10 to 100 nm, and at least one pigment dispersant of the formula (II)

in which
CPC is a residue of a copper phthalocyanine,
n is a number from 0.1 to 4, preferably 0.2 to 2,
m is a number from 0.1 to 4, preferably 0.2 to 2,
Kat is a cation from the group of alkali metals or H ⁺ ;
0 is a number from 0 to 3.9, preferably from 0 to 1.8, where n = m + o;
R ¹ , R ² , R ³ , R ⁴ independently of one another are each hydrogen, or a radical from the group C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₅ -C ₂₀ -cycloalkyl, C ₅ -C ₂₀ -cycloalkenyl, C ₁ -C ₄ -alkyl-phenyl, where the abovementioned radicals are optionally branched and are optionally substituted by sulfo, carboxy, hydroxy and halogen,
with the proviso that one, two or three of the radicals R ¹ to R ^{4 are} hydrogen.

Preference is given to pigment preparations in which CPC is a radical of the formula (I)

Preference is furthermore given to pigment preparations in which
R ¹ , R ² and R ^{3 are} hydrogen, and
R ⁴ is a radical from the group C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₅ -C ₂₀ cycloalkyl, C _5- C ₂₀ cycloalkenyl, C ₁ -C ₄ alkyl-phenyl, wherein the abovementioned radicals are optionally branched and are optionally substituted by sulfo, carboxy, hydroxy and halogen,
m is a number from 0.1 to 4, preferably 0.2 to 2,
Kat is a cation from the group H ⁺ , Li ⁺ , Na ⁺ and K ⁺ ;
n is a number from 0.1 to 4, preferably 0.2 to 2,
o is a number from 0 to 3.9, preferably from 0 to 1.8.

The radicals R ¹ , R ² , R ³ and R ⁴ have as preferred meaning C ₆ -C ₂₀ alkyl, C ₆ -C ₂₀ alkenyl and benzyl. with the proviso that one, two or three, in particular three, of the radicals R 1 to R 4 are hydrogen.

Examples of particularly preferred ammonium radicals NR1R2R3R4 ⁺ are primary ammonium radicals, such as n-hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Nonadecyl, eicosyl ammonium, their monounsaturated radicals, benzyl, 2-phenylethyl ammonium; secondary ammonium radicals such as dibutyl, dihexyl, dioctyl, didecyl, 2-ethyl-hexyl, dioleyl, distearyl, dibenzyl ammonium; tertiary ammonium radicals such as dimethyloctyl, dimethyldecyl, dimethyllauryl, dimethylstearyl, trioctyl, tribenzyl, bis (2-hydroxyethyl) dodecylammonium.

In the pigment preparations of the invention the weight ratio of C.I. Pigment Blue 15: 6 to pigment dispersant of formula (II) preferably between (97 to 3) and (70 to 30), especially preferably between (95 to 5) and (80 to 20).

The pigment preparations according to the invention contain the base pigment having an average particle size d ₅₀ of 10 to 100 nm, preferably 20 to 50 nm. The particle size distribution of CI Pigment Blue 15: 6 is preferably approximated to a Gaussian distribution. Thus, the ratio of d ₉₅ / d _{50 is} preferably less than 4.0: 1, more preferably less than 3.0: 1. The primary particles of the base pigment should have a length to width ratio of preferably less than 3.0: 1, more preferably less than 2.0: 1.

worin
R¹¹, R¹², R¹³, R¹⁴, R¹⁵ und R¹⁶ unabhängig voneinander Wasserstoff; C₁-C₂₂ Alkyl oder C₂-C₂₂ Alkenyl, deren Kohlenstoffkette jeweils durch eine oder mehrere Gruppierungen -O-, -S-, -NR⁹-, -CO- oder SO₂- unterbrochen sein kann und/oder ein- oder mehrfach durch Hydroxy, Halogen, Aryl, Heteroaryl, C₁-C₄ Alkoxy und/oder Acetyl substituiert sein kann;
C₃-C₈-Cycloalkyl, dessen Kohlenstoffgerüst durch eine oder mehrere Gruppierungen -O-, -S-, -NR¹⁰-, -CO- oder SO₂- unterbrochen sein kann und/oder ein- oder mehrfach durch Hydroxy, Halogen, Aryl, Heteroaryl, C₁-C₄-Alkoxy und/oder Acetyl substituiert sein kann; Dehydroabietyl oder Aryl oder Heteroaryl, wobei
R⁹ und R¹⁰ unabhängig voneinander Wasserstoff oder C₁-C₂₂–Alkyl bedeuten, oder wobei R¹³, R¹⁴, R¹⁵ und R¹⁶ eine Polyoxyalkylenkette, die gegebenenfalls endständig alkyliert ist, bedeuten.The pigment preparation according to the invention can furthermore contain 0.5 to 15% by weight, preferably 1 to 10% by weight, in particular 2 to 5% by weight, of an additive of the formula (3), based in each case on the weight of CI Pigment Blue 15: 6, included,

wherein
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 are} independently hydrogen; C ₁ -C ₂₂ alkyl or C ₂ -C ₂₂ alkenyl, the carbon chain of which may each be interrupted by one or more groups -O-, -S-, -NR ⁹ -, -CO- or SO ₂ - and / or a or may be substituted several times by hydroxy, halogen, aryl, heteroaryl, C ₁ -C ₄ alkoxy and / or acetyl;
C ₃ -C ₈ -cycloalkyl whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -NR ¹⁰ -, -CO- or SO ₂ - and / or mono- or polysubstituted by hydroxyl, halogen, Aryl, heteroaryl, C ₁ -C ₄ alkoxy and / or acetyl may be substituted; Dehydroabietyl or aryl or heteroaryl, wherein
R ⁹ and R ¹⁰ independently of one another are hydrogen or C ₁ -C ₂₂ -alkyl, or where R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 are} a polyoxyalkylene chain which is optionally terminally alkylated.

Aryl is preferably C ₆ -C ₁₀ -aryl, in particular phenyl or naphthyl. Heteroaryl means preferably a five- or six-membered heteroaromatic ring having 1, 2, 3 or 4 heteroatoms from the group N, O and S, which is optionally benzoannelated.

R ¹¹ , R ¹² , R ¹⁴ and R ^{16 are} preferably hydrogen.

R ¹³ and R ^{15 are} preferably (C ₂ -C ₄ -alkylene) -O- (C ₁ -C ₁₆ -alkyl).

wobei
R¹⁷ und R¹⁸ unabhängig voneinander Wasserstoff; C₁-C₁₉ Alkyl oder C₂-C₁₉ Alkenyl, deren Kohlenstoffkette jeweils durch eine oder mehrere der Gruppierungen -O-, -S-, -NR⁹-, -CO- oder SO₂- unterbrochen sein kann und/oder ein- oder mehrfach durch Hydroxy, Halogen, C₁-C₄ Alkoxy und/oder Acetyl substituiert sein kann, oder ein Rest der Formel -(AO)_n-Z, wobei A Ethylen oder Propylen ist, Z Wasserstoff oder C₁-C₁₆-Alkyl, und n eine Zahl von 1 bis 200, bevorzugt 10 bis 100, ist;
C₃-C₈-Cycloalkyl, dessen Kohlenstoffgerüst durch eine oder mehrere Gruppierungen -O-, -S-, -NR¹⁰-, -CO- oder SO₂- unterbrochen sein kann und/oder ein- oder mehrfach durch Hydroxy, Halogen, C₁-C₄-Alkoxy und/oder Acetyl substituiert sein kann; wobei R⁹ und R¹⁰ unabhängig voneinander Wasserstoff oder C₁-C₂₂-Alkyl bedeuten.A preferred additive for the purposes of the present invention is a compound of the general formula (4)

in which
R ¹⁷ and R ^{18 are} independently hydrogen; C ₁ -C ₁₉ alkyl or C ₂ -C ₁₉ alkenyl, the carbon chain of which may each be interrupted by one or more of the groupings -O-, -S-, -NR ⁹ -, -CO- or SO ₂ - and / or a - or may be substituted several times by hydroxy, halogen, C ₁ -C ₄ alkoxy and / or acetyl, or a radical of the formula - (AO) _n -Z, where A is ethylene or propylene, Z is hydrogen or C ₁ -C ₁₆ -Alkyl, and n is a number from 1 to 200, preferably from 10 to 100;
C ₃ -C ₈ -cycloalkyl whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -NR ¹⁰ -, -CO- or SO ₂ - and / or mono- or polysubstituted by hydroxyl, halogen, C ₁ -C ₄ alkoxy and / or acetyl may be substituted; where R ⁹ and R ¹⁰ independently of one another are hydrogen or C ₁ -C ₂₂ -alkyl.

For the purposes of the present invention, the additive of the formula (5) is particularly preferred.

additives of the formula (3), (4) and (5) can be known per se Manner by reacting naphthyl diisocyanate with the corresponding Amines are produced.

The Pigment preparations according to the invention can in addition to the phthalocyanine pigment and the pigment dispersant still common Auxiliaries or additives, such as surfactants, dispersants, Fillers, extenders, resins, waxes, defoamers, Anti-dust agents, extenders, antistatic agents, preservatives, drying retardants, Wetting agents, antioxidants, UV absorbers and light stabilizers, preferably in an amount of 0.1 to 10 wt .-%, in particular 0.5 to 5 wt .-%, based on the total weight of the pigment preparation.

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, alkylsulfosuccinates, Fatty Sarcosides; Fatty acids, for example Palmitic, stearic and oleic acid; the salts of these anionic substances and soaps, for example alkali 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.

to Achieving the desired fineness can be commercial available, usually coarsely divided epsilon-copper phthalocyanine with a crystalline inorganic salt in the presence of an organic Solvent be kneaded.

Such salt kneading are known in the art and, for example, in the WO 02/04563 A1 described.

The after kneading, finely divided C.I. Pigment Blue 15: 6 is isolated preferably after filtration as a filter cake or as a dried one Material of a post-treatment for applying the pigment dispersant (II) subjected.

object The invention also provides a process for the preparation of the invention Pigment preparation, characterized in that C.I. Pigment Blue 15: 6, optionally in the presence of the additive of formula (3), (4) or (5), before, during or after kneading, wet grinding, Dry grinding or finish treatment with the pigment dispersant of the formula (II). Preference is given to the treatment of finely divided Pigment Blue 15: 6 after kneading, wet grinding, dry grinding or finish treatment with the pigment dispersant of the formula (II).

For example can dry components in granular or powder form mixed before or after grinding; the one component can be added to the other component in wet or dry form be, for example, by mixing the components in the form of moist press cake.

The Mixing can be done, for example, by milling in dry form, in moist form, for example by kneading, or in suspension or by a combination of these methods. The grind can with the addition of water, solvents, acids or grinding aids such as salt.

at The drying of the wet pigment preparation, the known drying units are used, such as drying cabinets, Paddle wheel dryer, tumble dryer, contact dryer, belt dryer, spinflash dryer and spray dryer.

The Allow pigment preparations of the invention in principle for pigmenting all high molecular weight organic Use materials of natural or synthetic origin, For example, of plastics, resins, paints, especially metallic paints, Paints, electrophotographic toners and developers, Electret materials, color filters and inks, inks. In particular, can be with the inventive Pigment preparations achieve hues in the blue range, which are in demand when used in color filters. Here they take care of high contrast and also satisfy the other, when used in Color filters put demands, such as high temperature stability or steep and narrow absorption bands.

Especially are the pigment preparations of the invention also as a colorant in ink-jet inks on watery and non-aqueous base, as well as in inks that after the hot-melt process, suitable.

Especially are the pigment preparations of the invention however, as a colorant for color filters, both for the additive as well as the subtractive color generation, such as in electro-optical systems such as television screens, LCD (liquid crystal displays), charge coupled devices, plasma displays or electroluminescent displays, which in turn are active (twisted nematic) or passive (supertwisted nematic) ferroelectric displays or light-emitting diodes, as well as colorants for electronic inks ("e-inks") or "electronic paper" ("e-paper").

at the production of color filters, both reflective and transparent Color filters, become pigments in the form of a paste or as pigmented Photoresists in suitable binders (acrylates, acrylic esters, polyimides, Polyvinyl alcohols, epoxies, polyesters, melamines, gelatin, caseins) to the respective LCD components (eg TFT-LCD = Thin Film Transistor Liquid Crystal Displays or z. B. ((S) TN-LCD = (Super) Twisted Nematic LCD) applied. In addition to a high thermal stability is for a stable paste or a pigmented photoresist also a high pigment purity requirement. In addition, you can the pigmented color filters also by ink jet printing process or other suitable printing methods.

The Blue hues of the pigment preparations according to the invention are especially suitable for the Color Filter color set Red-Green-Blue (R, G, B). These three colors are separated Color dots next to each other in front, and are illuminated from behind a full color picture.

typical Colorants for the blue color point are phthalocyanine colorants or Benzimidazolondioxazinpigmente such. B. C.I. Pigment Blue 15: 6 and C.I. Pigment Blue 80. For the green Color point, phthalocyanine colorants are typically used, such as C.I. Pigment Green 36 and C.I. Pigment Green 7 and for the red color point are pyrrolopyrrole, quinacridone and azo pigments, such as C.I. Pigment Red 254, C.I. Pigment Red 209, C.I. Pigment Red 175 and C.I. Pigment Orange 38, single or mixed, common.

at Need can the respective color dots even more colors be added for nuancing. For the red and green color is preferably blended with yellow, for example with C.I. Pigment Yellow 138, 139, 150, 151, 180 and 213. For the blue hue is preferably mixed with Violet, z. With C.I. Pigment Violet 19 or 23.

To determine the brilliance and contrast ratio, a millbase is prepared. This is a 15% suspension of the pigment preparation in 66.25% PGMEA (propylene glycol monomethyl ether acetate), which in the presence of a commercially available, high molecular weight block copolymer (18.75% Disperbyk ^® 161 or 2001, Byk Chemie) Paint Shaker (Disperse ^® THE 200 of the company Lau GmbH) is dispersed for 5 h. The Millbase obtained in this way is measured with a Haake RS75 cone-plate viscometer at 20 ° C. ( DIN 53019 ). The stability of the Millbase is determined by measuring the viscosity after 7 days of storage.

20 g of the resulting Millbase be with 30.75 g of a 10% solution of a commercially available acrylate resin (Joncryl ^® 611 from Jonson Polymers) for 10 min. in a paint shaker Disperse (Disperse THE ^® 200 from Lau GmbH) is dispersed and there is obtained a resin base (RB).

to Determination of the contrast ratio and the brilliance becomes the described Resinbase (RB) with the help of a Spincoaters (POLOS Wafer Spinner) on glass plates (SCHOTT, laser cut, 10 × 10 cm) and at a layer thickness of 500 to 1300 nm, the contrast value (TSUBOSAKAELECTRIC CO. LTD, Model CT-1). The contrast values are set to one layer thickness normalized by 1000 nm and relatively compared (Table 2).

For the particle size distribution, a series of electron micrographs is used. The primary particles are visually identified. The area of each primary particle is determined using a graphic tablet. From the area of the diameter of the same area circle is determined. The frequency distribution of the equivalent diameters thus calculated is determined and the frequencies are converted into volume fractions and displayed as a particle size distribution. The d ₅₀ value indicates the equivalent diameter, for which 50% of the counted particles are smaller. The d ₉₅ value is defined analogously.

In In the following examples, percentages are by weight and parts by weight unless otherwise stated.

Example 1:

Production of fine-particle epsilon-copper phthalocyanine

A 2.5 L laboratory kneader (Werner & Pfleiderer) was determined with 187.5 parts commercial epsilon-copper phthalocyanine (d ₅₀ > 100 nm, length / width> 5: 1), 1125 parts NaCl (average particle size about 6 microns by laser diffraction) and 308 parts of diethylene glycol. The mixture was kneaded at about 80 ° C for 24 h. After completion of the kneading, the kneading mass was stirred with 11.25 L of dilute hydrochloric acid (5% strength by weight) for 2 hours at room temperature. After this solvent treatment, the suspension was filtered off and the filter cake was washed with water at 50.degree. 676 parts of aqueous filter cake (pigment content 27%) were obtained. The filter cake was used to prepare the pigment preparation of the invention.

Example 2:

1054 parts of epsilon-copper phthalocyanine filter cake from Example 1, corresponding to 268 parts of Cu phthalocyanine, were dispersed in 4290 parts of deionized water at 60 ° C. (pigment content of the suspension about 5%). Subsequently, a suspension of 21.4 parts of a copper phthalocyanine sulfonic acid (degree of sulfonation about 1.5) in 400 parts of deionized water / sodium hydroxide at a pH of 10.5 ± 0.5 was added to the pigment suspension. It was stirred for 30 minutes at 60 ° C and then added a solution of 9.4 parts of a coconut fatty amine (Genamin ^® CC100D, Clariant products (Germany) GmbH) in 250 parts of deionized water and 3 parts of glacial acetic acid. The mixture was stirred at 60 ° C. for a further 30 minutes, adjusted to a pH of 7.0 ± 0.5 with acetic acid, and the pigment suspension was filtered and washed at 50 ° C. with deionized water. After drying in a convection oven at 80 ° C. and pulverizing in a powder mill, 288 parts of a pigment preparation (dispersant content: 11.5%) were obtained. The particle size distribution of the fine-particle epsilon-copper phthalocyanine pigment preparation was determined by means of transmission electron microscopy (TEM) (see Table 1).

Example 3:

949 parts of epsilon-copper phthalocyanine filter cake from Example 1, corresponding to 255 parts of Cu phthalocyanine, were dispersed in 3860 parts of deionized water at 60 ° C. (pigment content of the suspension about 5%). Then, a suspension of 15.3 parts of a copper phthalocyanine sulfonic acid (degree of sulfonation about 1.5) in 400 parts of deionized water / sodium hydroxide at a pH of 10.5 ± 0.5 was added to the pigment suspension. It was stirred for 30 minutes at 60 ° C and then added a solution of 6.7 parts of a coconut fatty amine (Genamin ^® CC100D Clariant products (Germany) GmbH) in 178 parts of deionized water and 2 parts of glacial acetic acid. The mixture was stirred at 60 ° C. for a further 30 minutes, adjusted to a pH of 7.0 ± 0.5 with acetic acid, and the pigment suspension was filtered and washed at 50 ° C. with deionized water. After drying in a convection oven at 80 ° C. and pulverizing in a powder mill, 252 parts of a pigment preparation (dispersant content: 8.6%) were obtained.

Example 4:

Analogous Example 2 was a pigment preparation of 40 parts epsilon-copper phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 0.8 parts of 2-ethylhexylamine. After drying and pulverization 43 parts of a pigment preparation (dispersant content 10%) receive.

Example 5:

Analogous Example 2 was a pigment preparation of 40 parts epsilon-copper phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 0.62 parts of n-hexylamine. After drying and pulverization 43 parts of a pigment preparation (dispersant content 9.6%) receive.

Example 6:

Analogous Example 2 was a pigment preparation of 40 parts epsilon-copper phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 0.75 parts of 2-phenylethylamine. After drying and 41 parts of a pigment preparation (dispersant content 9.9%).

Example 7:

Analogous Example 2 was a pigment preparation of 40 parts epsilon-copper phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 1.21 parts of dibenzylamine. After drying and pulverization were 40 parts of a pigment preparation (dispersant content 11%) receive.

Example 8:

Analogous Example 2 was a pigment preparation of 40 parts epsilon-copper phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 2.17 parts of trioctylamine. After drying and pulverization 44 parts of a pigment preparation (dispersant content 13.4%) receive.

Example 9:

Analogous Example 2 was a pigment preparation of 40 parts epsilon-copper phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 1.77 parts tribenzylamine. After drying and pulverization 45 parts of a pigment preparation (dispersant content 12.4%) receive.

Example 10:

Analogous Example 2 was a pigment preparation of 40 parts Cu phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 1.64 parts of oleylamine. After drying and pulverization 45 parts of a pigment preparation (dispersant content 12.1%) receive.

Example 11:

Analogous Example 2 was a pigment preparation of 40 parts Cu phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 1.8 parts of coconut oil bis (2-hydroxyethyl) amine. After drying and pulverizing were 43 parts of a pigment preparation (Dispersatorgehalt 11%).

Example 12:

Analogous Example 2 was a pigment preparation of 40 parts Cu phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 2.17 parts of triisooctylamine. After drying and pulverization 45 parts of a pigment preparation (dispersant content 13.4%) receive.

Example 13:

Analogous Example 2 was a pigment preparation of 40 parts Cu phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 1.82 parts dehydroabietylamine. After drying and pulverization 44 parts of a pigment preparation (dispersant content 12.5%) receive.

Example 14:

Analogous Example 2 was a pigment preparation of 40 parts Cu phthalocyanine as a filter cake, 3.2 parts of Cu phthalocyanine sulfonic acid and 0.81 parts of 6-aminohexanoic acid. After drying and pulverizing, 41 parts of a pigment preparation (dispersant content 10%).

Example 15:

To a 1 liter flask was added 24 grams of a 9/1 mixture of powdered alpha / epsilon-copper phthalocyanine (dry pre-ground in a vibratory mill, unfinished), 1 gram of the additive of the formula

217 g of tetrahydrofuran and 256 g of dilute sulfuric acid (5 wt .-% strength) homogeneously mixed with stirring. Subsequently the mixture was refluxed for 6 hours. After this Solvent treatment, the suspension was filtered off, the presscake washed with water at 50 ° C, in one Convection oven for 18 h at 60 ° C and dried with a IKA mill pulverized. This gave 22.4 g of a pigment blue 15: 6 composition, according to example 1 and example 2 was treated.

Comparative Example 1 (according to WO 02/48269 ):

148 Parts of epsilon-copper phthalocyanine filter cake from Example 1 were in 710 parts of deionized water at 60 ° C dispersed (Pigment content of the suspension about 5%). Subsequently was a suspension of 2.47 parts of a copper phthalocyanine sulfonic acid (Degree of sulfonation about 1.5) in 50 parts of deionized water / sodium hydroxide at a pH of 10.5 ± 0.5 to the pigment suspension where. It was stirred at 60 ° C for 30 minutes and then at pH 7.0-7.5 became a solution of 1.93 parts of trioctylmethylammonium chloride in 40 mL of deionized Water is added to the suspension. It was added for another 30 minutes Stirred 60 ° C and the pigment suspension was filtered and washed at 50 ° C with deionized water. After drying in a convection oven at 80 ° C (12 h) and pulverizing in a powder mill were 44 parts of a pigment preparation (dispersant content: 11%).

Comparative Example 2 (according to WO 02/48268 )

146 parts of epsilon-copper phthalocyanine filter cake from Example 1 were dispersed in 700 parts of deionized water at 60 ° C. (pigment content of the suspension about 5%). Then, a suspension of 1.8 parts of a copper phthalocyanine sulfonic acid (degree of sulfonation about 1.5) in 36 parts of deionized water / sodium hydroxide at a pH of 10.5 ± 0.5 was added to the pigment suspension. It was stirred for 30 minutes at 60 ° C and then at pH 7.0-7.5, a solution of 1.4 parts of oleyl-bis (2-hydroxyethyl) methylammonium chloride in 20 parts of deionized water in 40 mL of deionized water to the Suspension given. The mixture was stirred for a further 30 minutes at 60 ° C, the pigment suspension was filtered and washed at 50 ° C with deionized water. After drying in a convection oven at 80 ° C. (12 hours) and pulverizing in a powder mill, 43 parts of a pigment preparation (dispersant content: 8%) were obtained. Table 1: sample d ₅₀ [nm] d ₉₅ / d ₅₀ Length Width Example 2 36 1.67 1.7: 1 starting material 120 1.62 5.1: 1 Table 2: sample Rel. Contrast ratio /% Comparative Example 1 100 Comparative Example 2 98 Example 2 108 Example 3 105 Example 4 108 Example 5 110 Example 6 112 Example 7 107 Example 8 108 Example 9 108 Example 10 110 Example 11 104 Example 12 109 Example 13 107 Example 14 106 Example 15 108

All Examples show what is needed for color filter applications high brilliance.

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

• - EP 0638615 A [0004]
• - JP 2005-234009 [0005]
• WO 02/48268 [0006, 0063]
• WO 02/48269 [0006, 0062]
• WO 02/04563 A1 [0029]

Cited non-patent literature

• - DIN 53019 [0042]

Claims (11)

Pigment preparation containing CI Pigment Blue 15: 6 with an average particle size d ₅₀ of 10 to 100 nm, and at least one pigment dispersant of the formula (II)

wherein CPC is a residue of a copper phthalocyanine, n is a number from 0.1 to 4, m is a number from 0.1 to 4, Kat is a cation from the group of the alkali metals or H ⁺ ; o is a number from 0 to 3.9, where n = m + o; R ¹ , R ² , R ³ , R ⁴ independently of one another are each hydrogen, or a radical from the group C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₅ -C ₂₀ -cycloalkyl, C ₅ -C ₂₀ -Cycloalkenyl, C ₁ -C ₄ alkyl-phenyl, wherein the aforementioned radicals are optionally branched and optionally substituted by sulfo, carboxy, hydroxy and halogen, with the proviso that one, two or three of the radicals R ¹ to R ^{4 is} hydrogen. Pigment preparation according to Claim 1, characterized that in formula (II) n represents a number from 0.2 to 2, m Represents number from 0.2 to 2 and 0 represents a number from 0 to 1.8, under the condition that n = m + o. A pigment preparation according to claim 1 or 2, characterized in that R ¹ , R ² and R ^{3 are} hydrogen, and R ^{4 is} a radical from the group C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₅ -C ₂₀ Cycloalkyl, C ₅ -C ₂₀ -cycloalkenyl, C ₁ -C ₄ -alkyl-phenyl, where the abovementioned radicals are optionally branched and are optionally substituted by sulfo, carboxy, hydroxy and halogen, m is a number from 0.1 to 4, Kat is a cation from the group H ⁺ , Li ⁺ , Na ⁺ and K ⁺ n is a number from 0.1 to 4, o is a number from 0 to 3.9. Pigment preparations according to one or more of claims 1 to 3, characterized in that the radicals R ¹ , R ² , R ³ and R ⁴ C ₆ -C ₂₀ alkyl, C ₆ -C ₂₀ alkenyl and benzyl. with the proviso that one, two or three of the radicals R ¹ to R ^{4 are} hydrogen. Pigment preparations according to one or more of Claims 1 to 4, characterized in that the weight ratio of C.I. Pigment Blue 15: 6 to pigment dispersant of the formula (II) between (97 to 3) and (70 to 30). Pigment preparation according to one or more of the claims 1 to 5, characterized in that the primary particles of the base pigment has a length to width ratio less than 3.0: 1. Pigment preparation according to one or more of Claims 1 to 6, characterized in that 0.5 to 15% by weight of an additive of the formula (3), based on the weight of CI Pigment Blue 15: 6, are present,

wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 are} independently hydrogen; C ₁ -C ₂₂ alkyl or C ₂ -C ₂₂ alkenyl, the carbon chain of which may each be interrupted by one or more groups -O-, -S-, -NR ⁹ -, -CO- or SO ₂ - and / or a or may be substituted several times by hydroxy, halogen, aryl, heteroaryl, C ₁ -C ₄ alkoxy and / or acetyl; C ₃ -C ₈ -cycloalkyl whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -NR ¹⁰ -, -CO- or SO ₂ - and / or mono- or polysubstituted by hydroxyl, halogen, Aryl, heteroaryl, C ₁ -C ₄ alkoxy and / or acetyl may be substituted; Dehydroabietyl or aryl or heteroaryl, wherein R ⁹ and R ^{10 are} independently hydrogen or C ₁ -C ₂₂ alkyl, or wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 is} a polyoxyalkylene chain which is optionally terminally alkylated. Process for the preparation of a pigment preparation according to one or more of claims 1 to 7, characterized characterized in that C.I. Pigment Blue 15: 6 before, during or after kneading, wet grinding, dry grinding or finish treatment with the pigment dispersant of formula (II). Use of a pigment preparation according to one or several of claims 1 to 8 for pigmenting high molecular weight organic materials natural or synthetic Origin. Use according to claim 9 for pigmenting Plastics, resins, paints, paints, electrophotographic Toners and developers, inks and inks. Use according to claim 9 or 10 for pigmenting from metallic paints, color filters and inkjet inks.