DE102004007382A1 - Black perylene pigments comprising fused-ring dipyridoperylenedione isomers useful for coloring high molecular weight organic material of natural and synthetic origin - Google Patents

Abstract

Black perylene pigments (I) comprising fused-ring dipyridoperylenedione isomers and having a black number of at least 210 in an alkyd/melamine stoving lacquer are new. Black perylene pigments (I) comprising fused-ring dipyridoperylenedione isomers of formula (Ia) and/or (Ib) and having a black number of at least 210 in an alkyd/melamine stoving lacquer are new. [Image] [Image] R 1>, R 2>phenylene, naphthylene or pyridylene, all optionally substituted with 1-12C alkyl, 1-6C alkoxy, OH, NO 2 and/or halo; X : halo; n : 0-4. Independent claims are also included for: (1) producing the perylene pigments from synthetically produced crude pigments by either comminution and optionally recrystallization from a liquid medium or comminution and simultaneous recrystallization; (2) producing the crude pigments by condensing perylene-3,4;9,10-tetracarboxylic acid dianhydride with an aromatic ortho-diamine and cyclizing the product, where condensation and cyclization are effected in a reaction medium comprising phenol or a non-fused nitrogen-containing heteroaromatic compound; (3) pigment synergists comprising isomers of formula (Ia') or (Ib'). [Image] [Image] R 1>', R 2>' : phenylene, naphthylene or pyridylene, all substituted with COOM, COOR 3>, CONR 3>R 4>, COO -> N +>R 3>R 4>R 5>R 6>, SO 2NR 3>R 4>, CH 2NR 3>R 4>, CH 2N +>R 3>R 4>R 5>R 6> R 3>COO -> and/or CH 2R 7> and optionally substituted with 1-12C alkyl, 1-6C alkoxy, OH, NO 2 and/or halo; R 3>-R 6>H; 1-12C alkyl or 2-12C alkenyl optionally interrupted by O, S, NR 8>, CO or SO 2 and optionally substituted with OH, halo, aryl, 1-4C alkoxy and/or acetyl; or 3-8C cycloalkyl optionally interrupted by O, S, NR 8> or CO and optionally substituted with acetyl; R 7>phthalimidyl; R 8>H or 1-8C alkyl; M : H or metal; X : halo; n : 0-4.

Description

in der die Reste R¹ und R² unabhängig voneinander Phenylen, Naphthylen oder Pyridylen, das jeweils ein- oder mehrfach durch C₁-C₁₂-Alkyl, C₁-C₆-Alkoxy, Hydroxy und/oder Halogen substituiert sein kann, bedeuten,
oder eine Mischung beider Isomere enthalten und eine Schwarzzahl ≥ 210 in einem Alkyd/Melamin-Einbrennlack aufweisen.The present invention relates to black perylene pigments which are one of the isomers of the formula Ia or Ib

in which the radicals R ¹ and R ^{2 are} independently phenylene, naphthylene or pyridylene, which may each be mono- or polysubstituted by C ₁ -C ₁₂ -alkyl, C ₁ -C ₆ -alkoxy, hydroxy and / or halogen .
or a mixture of both isomers and have a black number ≥ 210 in an alkyd / melamine stoving lacquer.

It also concerns the invention relates to the preparation of perylene pigments and their use for coloring of high molecular weight organic and inorganic materials more natural and synthetic origin, in particular paints, printing inks, Inks, polymers, paints, plastic articles, glasses, silicate Layer systems and organic-inorganic composites.

Around Paints, printing inks, plastics and glasses or other materials to color black are usually the black pigments soot, Aniline black, iron oxide black and chromium oxide black or trichrome Dye mixtures used.

The previously named pigmentary Colorants absorb light at wavelengths from ultraviolet to deep the far infrared range, so also the solar infrared and heat radiation. Materials colored with these black pigments, heat Therefore, very strong under direct sunlight. Become these conventional black pigments as colorants in coatings for electronic Components, as used in the Black Matrix LC displays, receives this Coating here also by a certain inherent electrical conductivity, the functionality of the electronic components adversely affected.

The Although trichromic dye mixtures have neither the unfavorable absorption in the infrared still high electrical conductivities, as low molecular weight However, compounds tend to migrate in the application medium and show low compatibility with many matrix materials (e.g., common polyolefins or water-based ones) Paints), so that their applications highly limited are.

In In recent years there has been a demand for black colorants, in particular Black pigments that do not have the mentioned unfavorable properties have, for many applications have risen sharply.

exemplary may be mentioned black coatings with high electrical resistance for electronic Components, black finishes and automotive coatings and construction area, which is not or only under sunlight warm little, Mulch and protective films with low self-heating for agriculture, optical Filters and IR-transparent active components for security printing and Copy protection systems.

Another interesting application is the laser transmission welding of plastic parts and foils. Plastic parts that are colored with the conventional black pigments can not be used for this purpose because the irradiated laser light whose wavelength is normally in the NIR range (eg at 808, 940 or 1064 nm), is completely absorbed by these pigments already on the surface of the workpiece to be irradiated, thus not reaching the deeper connection region and consequently no longer induce the melting process required to create a mechanically stable connection in this zone can.

meanwhile are black pigments based on perylene (C.I. Pigment Black 31 and 32 (N, N'-diphenylethyleneperylene-3,4: 9,10-tetracarboxylic diimide or N, N'-di (p-methoxytolyl) perylene-3,4: 9,10-tetracarboxylic acid diimide) available, which are NIR-transparent, but their absorption band at about 650 to 700 nm so that they are not visible throughout Absorb spectral range. These pigments therefore do not appear neutral black, but show especially in the whitening an undesirable Greenish tint. In addition, they show an increased solubility in many application media and insufficient temperature stability, indicating their applicability especially in the plastic coloring heavily limited.

WO-A-03/10241 and 03/10242 describe perylene pigments of the formula Ib defined at the outset as well as mixtures of pigments of the formulas Ia and Ib (R ¹ , R ² = phenylene), which, however, differ in their physical properties from the compounds according to the invention Distinguish pigments. Thus, the pigments prepared by dry calcination show only insufficient blackness (ie, black numbers ≦ 200), which is why the black Purton colorations obtained with them have a pronounced green or brownish tinge. In addition, these pigments are very hard to disperse, ie in the application medium only with high energy input and only partially disseminated, which adversely affects the transparency and homogeneity of the resulting colorations.

Of the The invention was therefore based on the object, the disadvantages mentioned to remedy and NIR-transparent black pigments high black grade to provide advantageous application properties.

in der die Reste R¹ und R² unabhängig voneinander Phenylen, Naphthylen oder Pyridylen, das jeweils ein- oder mehrfach durch C₁-C₁₂-Alkyl, C₁-C₆-Alkoxy, Hydroxy und/oder Halogen substituiert sein kann, bedeuten,
oder eine Mischung beider Isomere enthalten und eine Schwarzzahl ≥ 210 in einem Alkyd/Melamin-Einbrennlack aufweisen.Accordingly, black perylene pigments have been found which are one of the isomers of the formula Ia or Ib

in which the radicals R ¹ and R ^{2 are} independently phenylene, naphthylene or pyridylene, which may each be mono- or polysubstituted by C ₁ -C ₁₂ -alkyl, C ₁ -C ₆ -alkoxy, hydroxy and / or halogen .
or a mixture of both isomers and have a black number ≥ 210 in an alkyd / melamine stoving lacquer.

Of the The term "mixture" is intended to be physical Mixtures as well as preferably solid solutions (mixed crystals) of Compounds Ia and Ib include.

The phenylene, naphthylene and pyridylene radicals R ¹ and R ² in the formulas Ia and Ib may be mono- or polysubstituted by C ₁ -C ₁₂ -alkyl, in particular C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkoxy, especially C ₁ -C ₄ alkoxy, hydroxy and / or halogen, in particular chlorine or bromine, be substituted.

Prefers however, the phenylene, naphthylene and pyridylene radicals are unsubstituted, where the phenylene and naphthylene radicals are preferred and the naphthylene radicals are particularly preferred.

The perylene pigments according to the invention absorb in the entire visible spectral range and are characterized by their high black level, ie in an alkyd / melamine stoving lacquer by a black number M _Y ≥ 210, preferably ≥ 230. Accordingly, they give deep black, neutral Purtonfärbungen. In the whitening, neutral shades of gray (eg perylene pigments Ia / Ib with R ¹ = R ² = naphthylene) to slightly to distinctly bluish tints (eg perylene pigments Ia / Ib with R ¹ = R ² = phenylene) are obtained. Of course, the dyeings can be nuanced in the usual way by small amounts of inorganic or organic pigments, which can be added during the pigment formation, already in the pigment synthesis or only the formed perylene pigment.

The Perylene pigments according to the invention are transparent in the NIR range, the transmission is accordingly generally> 80%.

she As a rule, they have a primary particle size ≦ 800 nm, preferably ≦ 500 nm, especially preferably <200 nm, and are dispersible, i. they have e.g. in the plastic coloring one dispersion harshness DH <5 according to DIN 53775, Sheet 7, on.

• a) zunächst einer Zerkleinerung und anschließend einer Rekristallisation in flüssigem Medium oder
• b) einer Zerkleinerung unter gleichzeitiger Rekristallisation unterzieht.

They can advantageously be prepared by the process according to the invention, which is characterized in that the crude pigments obtained in the synthesis

• a) first a comminution and then a recrystallization in liquid medium or
• b) subject to comminution with simultaneous recrystallization.

The preparation of the crude pigments used in the preparation of the perylene pigments of the invention can in generally known manner by condensation of perylene-3,4: 9,10-tetracarboxylic acid (dianhydride) with the corresponding aromatic diamine at elevated temperature (eg 150 to 250 ° C) in a high-boiling organic solvent, such as nitrobenzene, tri- and dichlorobenzene, α-chloronaphthalene, choline, tetralin, N-methylpyrrolidone, N, N-dimethylformamide, ethylene glycol, glacial acetic acid and cyclic urea derivatives, carried out (see, eg CH 373 844 . GB 972 485 JP-A-07-157 681).

The Reaction takes place in two steps. In the first step reacts only one of the two amino groups to the associated diimide, the ring closure in the second Reaction step takes place after a long time Heating and can be achieved by adding a catalyst such as zinc chloride, Zinc acetate, zinc oxide, acetic acid, Hydrochloric acid, p-toluenesulfonic acid or an amine, e.g. Piperazine, be accelerated.

Particularly advantageous in the pigment formation, the crude pigments are used, which by the process according to the invention by condensation of perylene-3,4: 9,10-tetracarboxylic dianhydride with an aromatic ortho- or peri-diamine, the arylene radical R ¹ or R ² (ie, for example, 1,2-phenylene, 1,2-, 2,3- and 1,8-naphthylene), and subsequent cyclization are obtained, which is characterized in that one carries out condensation and cyclization in phenol as the reaction medium.

condensation and, above all, cyclization are much easier in phenol than in the solvents used in the known processes, so that one Reaction temperatures in the range of 140 to 190 ° C, in particular 160 to 180 ° C, can choose without lengthened Reaction times have to be accepted. So are the usual reaction times for the inventive method at about 3 to 8 h.

In usually 1.5 to 5 g, preferably 2 to 4 g, phenol depending g perylene pigment used.

If desired, Can the reaction mixture one of the above catalysts added, with piperazine being preferred. Usual amounts used amount then 0.1 to 1.35 moles of catalyst per mole of product.

In terms of process technology, the process according to the invention for preparing the perylene crude pigments is carried out as follows:
A stirred phenol melt of about 50 to 70 ° C is added, added perylene-3,4: 9,10-tetracarboxylic dianhydride, catalyst and aromatic diamine and heated for 2 to 8 h to the desired reaction temperature in the range of 140 to 190 ° C. , In this case, the resulting reaction water distils off as an azeotrope with phenol. To dilute the mixture is added after cooling to about 60 to 130 ° C, a lower aliphatic alcohol, for example methanol, and stirred for about 1 to 2 h at 40 to 65 ° C after.

The Isolation of Perylenrohpigments can then as usual by filtration, washing and drying.

The obtained here and also in the known production processes Raw pigments fall in the form of large ones Crystals usually very heterogeneous shape or as teilamorphe Powder on.

A particularly suitable embodiment for the Variant a) of the abovementioned production process according to the invention is that one the raw pigments first a dry grinding in the presence or absence of a salt as a grinding aid and then a recrystallization in an organic solvent, if desired in a mixture with water, in the heat subjects.

For dry grinding For example, ball mills, vibrating mills, planetary mills and Attrition. Suitable grinding media are e.g. Steel balls, silicon / aluminum / zirconia beads, glass beads and Agate balls, usually have a diameter in the range of 0.1 to 5 cm.

Out security It may be advantageous to carry out the grinding under an inert gas atmosphere.

The Dry grinding can also be carried out in the form of salt grinding. The grinding aids used are water-soluble inorganic salts, the at least one solubility of 10 g / 100 ml of water. Preferred salts are e.g. Aluminum sulfate, Sodium sulfate, sodium carbonate, calcium chloride, potassium chloride and Sodium chloride, with or without water of crystallization, with sodium sulphate, Potassium chloride and sodium chloride are particularly preferred. For removal of the salt, the ground material is stirred in water, filtered off and washed.

If desired, For example, the millbase obtained during grinding with steel balls can be removed for removal possibly existing iron abrasion subjected to a post-treatment with hydrochloric acid become.

Preferably is ground until the millbase has a mean primary particle size <30 nm.

When liquid Medium for the subsequent one Recrystallization can be a variety of organic solvents be used.

suitable solvent are e.g. Alcohols, ether alcohols, ethers, ketones, aliphatic carboxylic acids, carboxylic acid amides, Carbonsäureester and hydrocarbons. Of course, mixtures of these solvent be used.

Specific examples of particularly suitable solvents are:
aliphatic and araliphatic, monohydric or polyhydric alcohols having up to 10 C atoms, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol, isoamyl alcohol, hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, Ethylene glycol, 1,2- and 1,3-propylene glycol, cyclohexanol, methylcyclohexanol, benzyl alcohol and 2-phenylethanol;
Mono- and di-C ₂ -C ₃ alkylene glycol mono C ₁ -C ₄ alkyl ethers such as ethylene glycol monomethyl, ethyl and butyl ethers and diethylene glycol monomethyl and ethyl ethers;
acyclic and cyclic aliphatic ethers having up to 10 carbon atoms, such as dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl and diethyl ether;
acyclic and cyclic aliphatic and araliphatic ketones of up to 10 carbon atoms, such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone and propiophenone;
aliphatic carboxylic acids having up to 4 C atoms, such as formic acid, acetic acid, propionic acid and butyric acid;
Amides and C ₁ -C ₄ -alkylamides of aliphatic carboxylic acids having up to 4 C-atoms, such as formamide, N, N-dimethyl and N, N-diethylformamide, N, N-dimethyl and N, N-diethylacetamide, N , N-dimethyl and N, N-diethylpropionamide and N-methylpyrrolidone;
Esters of aromatic carboxylic acids having a total of up to 12 carbon atoms, such as dimethyl phthalate and diethyl phthalate;
alicyclic and aromatic hydrocarbons such as cyclohexane, benzene, toluene, xylene (all isomers), mesitylene (all isomers), ethylbenzene, chlorobenzene, o-dichlorobenzene, trichlorobenzene, nitrobenzene, naphthalene and methylnaphthalene, tetrahydronaphthalene and decahydronaphthalene.

Preferably, such solvents are used for the recrystallization, which can be easily removed in the workup, for example by washing with water, azeotropic distillation with water, water steam distillation or by drying the entire batch (for example by distilling off the solvent).

Particular preference is given to using those solvents which have a boiling point of ≦ 150 ° C. and can be evaporated without decomposition and without residue, for example C ₁ -C ₅ -alkanols, ketones, such as methyl ethyl ketone, ethers, such as tetrahydrofuran and dioxane, and hydrocarbons, such as cyclohexane , Benzene, toluene, xylene and chlorobenzene, and mixtures thereof, with xylene and toluene being most preferred.

All Particularly preferred are mixtures of organic solvent and water.

The Amount of solvent is generally not critical and can be within wide limits be varied. As a rule, 3 to 20 g, preferably 4 up to 15 g, solvent per grind of regrind used.

Usually take the recrystallization at a temperature of 25 to 200 ° C, especially 60 up to 180 ° C, in front.

The Recrystallization can be done by dispersing the millbase in the solvent or by simply leaving the millbase in the solvent respectively. The mixture of millbase and solvent is preferred touched.

The Duration of recrystallization depends from the temperature and the solvent from. It usually ends in 1 to 24 hours.

A particularly suitable embodiment for the Variant b) of the abovementioned production process according to the invention is that one the crude pigments in the presence of a recrystallizing acting organic solvent and an inorganic salt is subjected to kneading in the heat.

The Kneading is preferred in common Twin-shaft kneaders performed, it can However, single-shaft kneaders, mixers or extruders can be used. Also possible is also the Verkollern.

When inorganic salt are suitable for the above for the dry Salt grinding called water-soluble Salts, in particular, e.g. Sodium chloride and sodium sulfate. Usually Technical salts with or without prior micronisation are used. Preferably, the salts have an average particle size of 5 up to 200 μm, be particularly preferably from 10 to 50 microns. Besides, they have only expediently a solubility of ≤ 100 mg / l, in particular ≤ 10 mg / l (each at 20 ° C), in the organic solvent, preferably, they are practically insoluble therein.

Also the organic solvent used in the kneading is preferred a solubility in water of at least 10 g / 100 ml and is preferably neutral, wherein Do not disturb acidic or basic impurities. In addition to the recrystallization Solvent classes listed in the first process variant are also Sulfones and sulfoxides as solvents for the Kneading suitable. Of course Again, the use of solvent mixtures possible.

When examples for particularly suitable solvents may be mentioned in detail: ethylene glycol, diethylene glycol, triethylene glycol, Dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, Cyclohexanone, diacetone alcohol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane and Dimethyl sulfoxide.

In the rule contains the kneading composition per g of crude pigment 0.5 to 2 g, preferably 0.6 to 1 g, organic solvent and 1 to 10 g, especially 3 to 8 g, of inorganic salt.

The Knettemperatur is generally from 20 to 180 ° C, preferably 80 to 150 ° C.

The Rotation speed is suitably chosen so that the plasticine homogeneous and with uniform shear is moved.

The Kneading time is usually at 0.5 to 24 h, especially 1 to 8 h.

The inorganic salt and the organic solvent can after the kneading be washed out with water.

A another embodiment for the Variant b) of the abovementioned production process according to the invention is that one the crude pigments of a wet grinding in the presence of a recrystallizing organic solvent, if desired in a mixture with water.

The wet milling can be advantageously carried out in a stirred ball mill become.

When organic solvent are in principle the for the variant a) mentioned solvents suitable, being water-soluble solvent are preferred.

Usually be 1 to 50 wt .-% of solvent, based on the raw pigment to be ground used.

Prefers becomes the wet grinding in aqueous medium carried out. Amount of water and solvent are thereby advantageously chosen that the Pigment content in the millbase at 5 to 20 wt .-% is.

The Grinding temperature is generally from 5 to 100 ° C, preferably 10 to 85 ° C.

The Perylene pigments according to the invention can advantageously also be prepared by the further process according to the invention, which is characterized in that in the synthesis obtained crude pigments, if desired after crushing, swelling in a concentrated acid.

For this the crude pigment becomes common for one certain time in the concentrated acid at a certain temperature touched. The approach will follow added to water, then the precipitated pigment is filtered off, washed, dried and pulverized.

Examples for suitable acids are in addition to organic acids, like trifluoroacetic acid, in particular concentrated inorganic acids such as polyphosphoric acid and especially sulfuric acid.

The used acid generally has a concentration of 50 to 90 wt .-%, preferably from 70 to 85 wt .-%, on.

Usually gets so much acid used that Pigment concentration at 5 to 20 wt .-%, in particular 7 to 15% by weight.

The Swelling is usually carried out at 20 to 100 ° C, preferably at 30 to 60 ° C, and is generally completed in 1 to 24 hours, especially in 4 to 12 hours.

to Control of crystal size can it may be advantageous to control the pigment formation, i. the transfer of the Crude pigments in the perylene pigments according to the invention, in the presence of pigment synergists, usually about 0.01 to 0.1 g synergist per g of pigment are used. The Pigments synergists can already in the pre-comminution step, but also only in the recrystallization step be added.

pigment synergists are compounds that are the pigment chromophore in whole or in part in their molecular structure contain. The must Structure of the pigment synergist not with the structure of the pigment, whose Crystallization affects should be consistent. So can in the present case, not only pigment synergists based on Perylene structure, but e.g. also those based on the copper phthalocyanine structure be used.

Particularly suitable pigment synergists can be based on one or both isomers of the formula Ia or Ib in which the radicals R ¹ and R ² contain one or more of the acid radicals -COO ^- M ⁺ , -COOR ³ , -COONR ³ R ⁴ , -COO ^- N ⁺ R ³ R ⁴ R ⁵ R ⁶ , -SO ₃ ^- M ⁺ , -SO ₂ NR ³ R ⁴ and / or -SO ₃ ^- N ⁺ R ³ R ⁴ R ⁵ R ⁶ as substituents.

M ⁺ stands for hydrogen or a metal cation, in particular an alkali metal cation, especially sodium or potassium.

R ³ , R ⁴ , R ⁵ and R ^{6 are} independently hydrogen; C ₁ -C ₁₂ -alkyl or C ₂ -C ₁₂ -alkenyl, whose carbon chain may be interrupted in each case by one or more groups -O-, -S-, -NR ⁷ -, -CO- or -SO ₂ - and / or or the one or more times by hydroxy, halogen, aryl, C ₁ -C ₄ alkoxy and / or acetyl may be substituted; C ₃ -C ₈ -cycloalkyl, whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -NR ⁷ - or -CO- and / or may be substituted by acetyl, where R ^{7 is} hydrogen or C C ₁ -C ₈ alkyl.

The The presence of pigment synergists often has a positive effect on the dispersibility and the flocculation stability of the perylene pigments according to the invention in the application medium and thus also on the rheology of the application medium, e.g. of a paint system, off.

The Dispersibility of Perenpigmente invention can also by occupying the pigment surface with conventional Additives are improved. In addition to additives based on rosin derivatives are especially for the plastic coloring Additives based on natural and synthetic waxes. Waxes are an example Base of polyethylene and polypropylene, which may also be oxidized can, polyethylene oxide, ethoxylated fatty alcohols, polyethylene oxide / polypropylene oxide / block copolymers, of fatty acid esters (e.g., montan waxes), fatty acid amides and of ethylene / vinyl acetate copolymers.

The Perylene pigments according to the invention are ideal for coloring high molecular weight organic and inorganic materials of natural and synthetic origin.

As examples of high molecular weight synthetic organic materials may be mentioned:
Polyolefins such as polyethylene, polypropylene, polybutylene, polyisobutylene, and poly-4-methyl-1-pentene, polyolefin copolymers, such as Luflexen ^® (Basell), Nordel ^® (Dow) and Engage ^® (DuPont), cycloolefin copolymers such as Topas ^® (Celanese) , Polytetrafluoroethylene (PTFE), ethylene / tetrafluoroethylene copolymers (ETFE), polyvinylidene difluoride (PVDF), polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl alcohols, polyvinyl esters such as polyvinyl acetate, vinyl ester copolymers such as ethylene / vinyl acetate copolymers (EVA), polyvinyl alkanals such as polyvinyl acetal and polyvinyl butyral (PVB), polyvinyl ketals, polyamides such as ^Nylon® [6], nylon [12] and nylon [6,6] (DuPont), polyimides, polycarbonate, polycarbonate copolymers and physical blends of polycarbonates with acrylic butadiene Styrene copolymers, acrylonitrile-styrene-acrylic ester copolymers, polymethyl methacrylates, polybutyl acrylates, polybutyl methacrylates, polybutylene terephthalates and polyethylene terephthalates, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), copolymers, transesterification products and physical blends of the aforementioned polyalkylene terephthalates, poly (meth) acrylates, polyacrylamides, polyacrylonitrile, poly (meth) acrylate / polyvinylidene difluoride blends, polyurethanes, Polystyrene, styrene copolymers such as styrene / butadiene copolymers, styrene / acrylonitrile copolymers (SAN), styrene / ethyl methacrylate copolymers, styrene / butadiene / ethyl acrylate copolymers, styrene / acrylonitrile / methacrylate copolymers, acrylonitrile / butadiene / styrene copolymers (ABS) and methacrylate / butadiene / styrene copolymers (MBS), polyethers such as polyphenylene oxide, polyether ketones, polysulfones, polyethersulfones, polyglycols such as polyoxymethylene (POM), polyaryls such as polyhenylene, polyarylenevinylenes, silicones, ionomers, thermoplastic and thermosetting polyurethanes and mixtures thereof ,

When colorable High molecular weight organic materials are not just the polymers in themselves ("plastics"), which are powders, plastic masses, melts or in the form of spinning solutions can, but also the paints, inks and paints, which dissolved or dissolved these materials dispersed form.

The Incorporation of the perylene pigments of the invention the plastics can be made by any known method, e.g. by common extrusion (preferably with one or twin-screw extruders), rolling, kneading, pressing or grinding, the plastics being transformed into plastic moldings, endless profiles, plates, Films, fibers, films and coatings can be processed.

As examples of high molecular weight synthetic inorganic materials are listed:
low-melting borosilicate glass frit, optionally organically modified silicate sols and gels, optionally doped silicate, aluminate, zirconate and aluminosilicate coatings and phyllosilicates prepared by a sol-gel process.

exemplary in the following are some selected, particularly interesting fields of application for the perylene pigments according to the invention called.

One interesting field is the use in security printing inks , e.g. Production and printing of banknotes, stocks, check forms, Credit cards, stamps, lottery tickets and tamper-proof ones Packaging, for example Pharmaceutical products and high quality branded products.

Particularly suitable for this purpose are the perylene pigments of the formula Ia and / or Ib according to the invention in which R ¹ and R ^{2 are} phenylene, since these pigments have a pronounced absorption in the visible range from 400 to 800 nm and in the NIR range (band edge about 850 nm ) are transparent. Likewise well suited are the perylene pigments of the formula Ia and / or Ib according to the invention in which R ¹ and R ^{2 are} naphthylene, which also absorb strongly in the visible range and become transparent in the NIR range (band edge about 950 nm).

The black prints prepared with these pigments are absorbed Viewing in NIR light transparent, i. they become invisible. So you can, for example, a motif printed with a conventional carbon black pigment overprint the IR transparent ink. When viewed in NIR light, the original motif becomes visible again.

The Incorporation of the perylene pigments of the invention in the binder systems of these security inks as well Any printing ink can be with usual Dispersing aggregates, e.g. Agitator ball mills or Roll mills, respectively. Also can all known printing methods, for example offset printing, gravure printing, High pressure, intaglio printing, screen printing and pad printing, applied become.

Furthermore, the perylene pigments according to the invention can also be advantageously used in paints and laminates in order to achieve better thermal protection in black and gray coatings or film coatings and in coatings or film coatings containing black pigments as a color mixture component. It must be ensured, that the IR radiation is reflected either by the coating layer or laminated film itself or by its substrate, which greatly by the addition of the IR-range scattering foreign particles such as titanium dioxide pigments and inorganic mixed phase pigments (eg Sicotan ^® pigments, BASF) or in the IR range strongly reflecting foreign particles, such as aluminum flakes and luster pigments, for example those based on coated aluminum platelets, the paint or lamination or a use of metallic or diffusely scattering white substrates is achieved.

In addition, the perylene pigments according to the invention, in particular the preferred perylene pigments (R ⁴ , R ² : phenylene or naphthylene), due to their very low electrical conductivity can be advantageously used as part of the color filter in LC displays. In these color filters, the red, green and blue color fields are separated by a black grid, the so-called black matrix. To this end, resist inks are produced with the perylene pigments according to the invention which, after application and curing with UV light, give a black matrix raster having the desired high resistance value of> 10 ¹³ Ω and high optical density with a small layer thickness.

by virtue of their NIR transparency the perylene pigments of the invention also excellent for black coloring of plastics, which are welded by the laser transmission method should be used.

For many Applications, it may be advantageous initially liquid water-based preparations of Perylene pigments according to the invention produce the water or mixtures of water and organic solvents as liquid Phase included.

Also advantageous is the use of previously separately prepared pigment preparations based on a polymer or a polymer blend, one or more polyolefin waxes or mixtures thereof to achieve homogeneous, strong colorations in low-melting polymers (eg most common polyolefins) or those with low melt viscosity (eg plasticized PVC and PVB as well as blow-molded PET). While the carrier polymer (blend) used in the polymer-based pigment preparations ("masterbatch", "compound") is generally identical to the high molecular weight synthetic organic material to be colored, homopolymeric and copolymeric PE and PP waxes are used to produce polyolefin wax-based pigment preparations as support material as Luwax ^® A (ethylene homopolymer; BASF), Luwax EVA (ethylene-vinyl acetate copolymer; BASF) or ^® Licowax PP 230 (propylene homopolymer; Clariant) use.

Production and testing of Perylene pigments according to the invention

A) Production

example 1

Perylene pigment II: cis / trans isomer mixture of the formula Ia / Ib (R ¹ = R ² = 1,2-phenylene)

a) Preparation of the crude pigment

In a stirred Melt of 318 g of phenol at 70 ° C. were 78.4 g of perylene-3,4: 9,10-tetracarboxylic dianhydride, Entered 16.3 g of piperazine and 51.9 g of o-phenylenediamine. After heating the mixture to 180 ° C was stirred for 8 h at this temperature. The resulting reaction water distilled off as an azeotrope with phenol.

To cooling down to 130 ° C, Slow dropwise addition of 350 g of methanol and stirring for one hour 60 ° C was the precipitated Filtered off, washed with methanol until a clear Filtrate was formed, dried in vacuo at 100 ° C and then pulverized.

It 106 g of a black powder were obtained in the form of acicular crystals from a size up to more than 10 microns.

b) pigment formation

50 g of the black powder obtained in step a) were in a with 2.6 kg steel balls (diameter 25 mm) filled 1.3 l vibration mill 10 h ground.

The Ground material was then after separation of the grinding balls in a mixture from 250 g of toluene and 250 g of water in an autoclave for 5 h at 150 ° C stirred. To azeotropic distilling off the toluene, the product was filtered off, washed with water and dried in a convection oven at 100 ° C. and then pulverized.

The obtained crystalline black perylene pigment II had a primary particle size in the range from 40 to 300 nm.

Example 2

Perylene pigment III: cis / trans isomer mixture of the formula Ia / Ib (R ¹ = R ² = 1,8-naphthylene)

a) Preparation of the crude pigment

In a stirred Melt of 265 g phenol at 70 ° C were 78.4 g of perylene-3,4: 9,10-tetracarboxylic dianhydride, Entered 16.3 g of piperazine and 75.9 g of 1,8-diaminonaphthalene. To Heat the mixture to 180 ° C was stirred for 8 h at this temperature. The resulting reaction water distilled off as an azeotrope with phenol.

To cooling down to 130 ° C, Slow dropwise addition of 350 g of methanol and stirring for one hour 60 ° C was the precipitated Filtered off, washed with methanol until a clear Filtrate was formed, dried in vacuo at 100 ° C and then pulverized.

It 125 g of a black powder were obtained in the form of acicular crystals of a size of 90 up to 300 nm.

b) pigment formation

50 g of the black powder obtained in step a) were in a with 2.6 kg steel balls (diameter 25 mm) filled 1.3 l vibration mill 10 h ground.

The Ground material was then after separation of the grinding balls in 700 g of xylene in an autoclave for 5 h at 180 ° C. touched. After distilling off the xylene in vacuo, the product was in a convection oven at 100 ° C dried and then pulverized.

The obtained crystalline black perylene pigment III had a primary particle size in the range from 30 to 150 nm.

Example 3

Perylene pigment III

a) Preparation of the crude pigment

The Preparation was carried out as described in Example 2a).

b) pigment formation

50 g of the black powder obtained in step a) were in a with 2.6 kg steel balls (diameter 25 mm) filled 1.3 l vibration mill 10 h ground.

The Ground material was then after separation of the grinding balls in 200 g of phenol 8 h at 180 ° C touched. To cooling down to 120 ° C, Add dropwise 450 ml of methanol and stirring for 2 hours 60 ° C was the Product filtered off, washed with 300 ml of methanol, in a convection oven at 100 ° C dried and then pulverized.

The obtained, in the form of uniform crystals present black perylene pigment III had a primary particle size in the range from 20 to 80 nm.

Example 4

Perylene pigment II

a) Preparation of the crude pigment

The Preparation was carried out as described in Example 1a).

b) pigment formation

12 g of the black powder obtained in step a) were mixed with 90 g Sodium chloride in one with 2.6 kg steel balls (diameter 25 mm) filled 1.3 l vibration mill Milled for 24 h at room temperature.

The Ground material was then in portions after separation of the grinding balls in a mixture of 1000 g of water and 200 g of conc. Hydrochloric acid registered and stirred for 1 h at room temperature. Thereafter, the black powder was filtered off and salt-free with water washed.

It were several approaches carried out and then mixed.

172 g of the water-moist press cake obtained (dry content 29%) were then mixed in a mixture of 250 g of toluene and 128 g of water in an autoclave for 5 h at 150 ° C touched. After azeotropic distilling off the toluene, the product was filtered off, washed with water, dried in a convection oven at 100 ° C. and then pulverized.

The obtained crystalline black perylene pigment II had a primary particle size in the range from 40 to 300 nm.

Example 5

Perylene pigment III

a) Preparation of the crude pigment

The Preparation was carried out as described in Example 2a).

b) pigment formation

50 g of the black powder obtained in step a) were in a with 2.6 kg steel balls (diameter 25 mm) filled 1.3 l vibration mill 10 h ground.

40 g of the resulting millbase were then after separation of the grinding balls swiftly in 305 g 80 wt .-% sulfuric acid given and 24 h at 25 ° C. touched. Subsequently the mixture was precipitated in 750 ml of water. The product was filtered off, washed neutral with water, dried in a convection oven at 100 ° C. and then pulverized.

The obtained, in the form of heterogeneous crystals present black perylene pigment III had a primary particle size in the range from 50 to 600 nm.

Example 6

Perylene pigment II

a) Preparation of the crude pigment

The Preparation was carried out as described in Example 1a).

b) pigment formation

35 g of the black powder obtained in step a) were mixed with 210 g sodium chloride and 40 g dipropylene glycol in a Doppelwellenkneter (Duplex, Fa. IKA) with a kneading volume of 0.3 l for 4 h at 100 ° C kneaded.

The Putty was added to 10 l of water and stirred for 30 min. The Product was then filtered off, washed free of salt with water, in Convection drying oven at 100 ° C dried and then pulverized.

The obtained, in the form of homogeneous crystals present black perylene pigment II had a primary particle size in the range from 30 to 150 nm.

Example 7

Perylene pigment III

a) Preparation of the crude pigment

The Preparation was carried out as described in Example 2a).

b) pigment formation

35 g of the black powder obtained in step a) were mixed with 210 g sodium chloride and 40 g dipropylene glycol in a Doppelwellenkneter (Duplex, Fa. IKA) with a kneading volume of 0.3 l for 4 h at 100 ° C kneaded.

The kneading material was introduced into 10 l of water and stirred for 30 min. The suspension was then, after adjusting to a pH of 11.2 with 10 wt .-% sodium hydroxide solution with 35 g of a 10 wt .-% solution of a polymerized rosin-based resin (Dertopol ^® , Willers, Engel & Co.) in 1.5 wt .-% sodium hydroxide added and adjusted after a stirring time of 15 min with 10 wt .-% hydrochloric acid to pH 2.5. After stirring for a further 20 minutes, the product was filtered off, neutralized with water Wash, dried in a convection oven at 100 ° C and then pulverized.

The obtained, in the form of homogeneous crystals present black perylene pigment III had a primary particle size in the range from 30 to 100 nm.

Example 8

Perylene pigment II

a) Preparation of the crude pigment

The Preparation was carried out as described in Example 1a).

b) pigment formation

12 g of the black powder obtained in step a) were mixed with 90 g Sodium chloride in one with 2.6 kg steel balls (diameter 25 mm) filled 1.3 1 swing mill Milled for 24 h at room temperature.

It were several approaches carried out and then mixed.

40 g of the resulting millbase were then after separation of the grinding balls swiftly in 400 g of 80% strength by weight sulfuric acid given and at 50 ° C for 24 h touched. Subsequently the mixture was precipitated in 2 l of water. The product was filtered off, washed neutral with water and then redispersed in 1 liter of water. The Suspension was then after adjusting to a pH of 9.8 with 10 wt .-% sodium hydroxide solution with 40 g of a 10 wt .-% solution of a polymerized rosin-based resin (Dertopol, Willers, Angel & Co) in 1.5 wt .-% sodium hydroxide added and after a stirring time of 15 min with 10 wt .-% hydrochloric acid adjusted to pH 2.5. After another 20minütigem stirring was The product is filtered off, washed neutral with water, in a circulating air dryer at 100 ° C dried and then pulverized.

The obtained, in the form of heterogeneous crystals present black perylene pigment II had a primary particle size in the range from 30 to 150 nm.

Example 9

Perylene pigment II in the mixture with C.I. Pigment Yellow 185

a) Preparation of Perylenrohpigments

The Preparation was carried out as described in Example 1a).

b) pigment formation

A Mixture of 41.7 g of the black powder obtained in step a) and 8.3 g C.I. Pigment Yellow 185 was in one with 2.6 kg steel balls (Diameter 25 mm) filled 1.3 l vibration mill Ground for 20 hours.

40 g of the resulting millbase were then after separation of the grinding balls in 240 g of xylene with stirring Heated under reflux for 3 h. After azeotroping the xylene, the product was in vacuo at 100 ° C dried and then pulverized.

The black powder obtained was predominantly in the form of crystals having a primary particle size of 40 to 400 nm.

B) Examination

B1) Determination of the black number

To determine the Purtonkoloristik was a mixture of 1.0 g of each pigment and 9.0 g of an alkyd / melamine stoving enamel (binder content of 43 wt .-%, adjusted with xylene to 35 wt .-%) with 10 ml glass beads (Diameter 3 mm) in a 30 ml glass bottle shaken for 60 min on a Skandex dispersing unit. The resulting paste was then applied as a 150 micron thick layer on a Kar clay applied, flashed off and baked at 130 ° C for 30 min.

After colorimetric evaluation with a spectrophotometer Spectraflash SF 600 plus (Datacolor) the black number was calculated according to the following formula from the standard color value Y: Black number = 100 × log (100 / Y)

The Black numbers determined are summarized in Table 1. To the Comparison are the analog for one carbon black pigment (Monarch 1400, Cabot Co.) (V1) and for the analogous example 2 of WO-A-03/10241 prepared isomer mixture (V2) determined black numbers recites.

Table 1

B2) Examination of heat development

Around the interior heating to simulate exposure to sunlight caused by sheets (standard construction: KTL layer plus standard filler painted) with black pigmented paints are coated, the painted sheets (colored pastes analog B1), but only 5% pigmented; Layer thickness only 30 μm) as cover placed with the painted side up on a Styrofoam box and according to the method described in EP-A-1 219 684 with a halogen lamp irradiated at a distance of 40 cm with a power of 750 W. The Internal temperature in the box was then after 10, 20, 30 and 35 min Irradiation measured.

The Measurement results are summarized in Table 2. For comparison, the for the primed sheet (V0) as well as for the analog using a carbon black pigment (Flammruß FW 200, Degussa) (V3) painted sheet metal included.

Table 2

These results show that in the coated with the perylene pigments of the invention compared to V3 a higher transmission in the IR region is present, resulting in a stronger reflection of the IR radiation on the ground and thus to a lower interior heating, so a better Thermal insulation, leads. The comparison with the primed sheet (V0) shows that the observed residual heating is almost exclusively due to the absorption of the IR radiation by the primer.

B3) Coloring of plastics

a) polyethylene-LD:

to Determination of the Purton Koloristik in PE-LD were the respective pigment and PE-LD powder (pigment concentration 0.2 wt .-%) mixed and on a mixing mill at a roll temperature of 160 ° C and 200 Roller revolutions processed to a rolled sheet of thickness 0.4 mm. The Rolled coat was subsequently pressed in a press with spacer frame (1 mm) at 180 ° C to plates.

The respectively obtained black-colored Plates were colorimetric using a spectrophotometer Spectraflash SF 600 plus (from Datacolor) evaluated.

The obtained measurement results are summarized in Table 3.

Table 3

b) polyethylene-HD and engineering plastics:

To determine the Purtonkoloristik in PE-HD (Lupolen ^® 6031 M; Basell), polypropylene (PP; Moplen ^® 466R; Basell), polycarbonate (PC; Makrolon ^® 2800 N; Bayer), polyamide [6] (PA 6; Ultramid ^® BS 700; BASF), acrylonitrile / butadiene / styrene copolymer (ABS; Terluran ^® GP 22; BASF) and polymethyl methacrylate (PMMA; Plexiglas 7N; Röhm) were the respective pigment and polymer (pigment concentration 0.2 wt .-%) in a glass bottle for 30 minutes on a roller board, once homogenized by a twin-screw extruder (ZSE 27 / GL-44D, Fa Leistritz) at the melt temperature T ₁ ° C indicated in Table 4 and granulated. The dyed granules thus obtained were then processed into platelets at an injection molding temperature of T ₂ ° C. using an injection molding machine (Allrounder, Arburg).

The respectively obtained black-colored spray plate were colorimetric with a spectrophotometer (Spectraflash SF 600 X; Fa. Datacolor) evaluated.

The obtained measurement results as well as according to DIN 53772 in white whitening 1:10 in the respective polymers certain temperature resistances TB [° C] are summarized in Table 4.

Table 4

B4) Coloring of varnishes

a) Determination of Purton Coloristics

According to B1) was prepared using the pigment of Example 3, a colored paste and painted.

The colorimetric evaluation of the black coating with a spectrophotometer Spectraflash SF 600 plus (Datacolor) gave the following measured values:
a * = 0.2; b * = -0.8

b) Coloristics in white whitening

1.6 g of the colored paste from B4a) were mixed with 1.0 g of a 40 wt .-% strength Titanium dioxide (Kronos 2310) pigmented white paste (whitening approx. 1/3 standard color depth) mixed than 150 μm thick layer applied to a box, ventilated and 30 min at 130 ° C baked.

The colorimetric evaluation of the gray coating with a spectrophotometer Spectraflash SF 600 plus (Datacolor) gave the following measured values:
a * = 5.3; b * = -14.4.

Claims (13)

Black perylene pigments which are one of the isomers of the formula Ia or Ib

in which the radicals R ¹ and R ^{2 are} independently phenylene, naphthylene or pyridylene, which may each be mono- or polysubstituted by C ₁ -C ₁₂ -alkyl, C ₁ -C ₆ -alkoxy, hydroxy and / or halogen , or contain a mixture of both isomers and have a black number ≥ 210 in an alkyd / melamine stoving lacquer. Perylene pigments according to Claim 1, in which the radicals R ¹ and R ^{2 are} identical and denote unsubstituted phenylene or naphthylene. Process for the preparation of perylene pigments according to claim 1 or 2, characterized in that in the synthesis obtained crude pigments a) first a crushing and subsequently a recrystallization in liquid Medium or b) comminution with simultaneous recrystallization subjects. Method according to claim 3, characterized that he the raw pigments first a dry grinding in the presence or absence of a salt as a grinding aid and then a recrystallization in an organic solvent, if desired in a mixture with water, in the heat subjects. Method according to claim 3, characterized that he the crude pigments in the presence of a recrystallizing acting organic solvent and an inorganic salt is subjected to kneading in the heat. Method according to claim 3, characterized that he the crude pigments of a wet grinding in the presence of a recrystallizing organic solvent, if desired in a mixture with water. Process for the preparation of perylene pigments according to claim 1 or 2, characterized in that in the synthesis obtained crude pigments, if desired after crushing, swelling in a concentrated Acid. A method according to claim 3 or 7, characterized in that the crude pigments by condensation of perylene-3,4: 9,10-tetracarboxylic dianhydride with an aromatic ortho- or peri-diamine having the arylene radical R ¹ or R ² , and subsequent cyclization in the presence of phenol produces. Process for the preparation of Perylenrohpigmenten, which is one of the isomers of the formula Ia or Ib

in which the radicals R ¹ and R ^{2 are} independently phenylene, naphthylene or pyridylene, which may each be mono- or polysubstituted by C ₁ -C ₁₂ -alkyl, C ₁ -C ₆ -alkoxy, hydroxy and / or halogen , or a mixture of both isomers, by condensation of perylene-3,4: 9,10-tetracarboxylic dianhydride with an aromatic ortho-diamine having the arylene radical R ¹ or R ² , followed by cyclization, characterized in that condensation and Cyclization in phenol as the reaction medium. Use of perylene pigments according to claim 1 or 2 for coloring of high molecular weight organic and inorganic materials more natural and synthetic origin. Use according to claim 10, characterized that varnishes, Printing inks, inks, polymers, paints, plastic articles, glasses, silicate layer systems and organic-inorganic composites are dyed. Use of perylene pigments according to claim 1 or 2 for coloring of plastic articles for the laser transmission welding be used. Use of perylene pigments according to claim 1 or 2 for the preparation of water, polymer or polyolefin wax-based Pigment preparations.