Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
  • C09B67/0015—Influencing the physical properties by treatment with a liquid, e.g. solvents of azoic pigments
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
  • C09B67/0016—Influencing the physical properties by treatment with a liquid, e.g. solvents of phthalocyanines

Definitions

• the present invention is in the field of organic colored pigments. It is known that organic pigments, in particular azo pigments, precipitate out of the synthesis solution in small, insoluble particles (primary crystallites) which still require post-treatment (finish). Physical properties such as crystal shape, crystal size and quality, and particle size distribution must be changed in the direction of a desired optimum. If you dry a raw pigment press cake immediately after synthesis and washing, the primary particles often accumulate to a considerable extent to form agglomerates and aggregates. This leads to hard-grain, weakly colored and poorly dispersible pigments, which can often no longer be brought into a form that can be used in technical applications.
• Polycyclic pigments usually precipitate out of the synthesis solution as coarse-crystalline raw pigments, which are then processed using suitable processes, e.g. Grinding, must be finely divided.
• suitable processes e.g. Grinding
• the prepigments obtained in this way also require aftertreatment in most cases in order to achieve the desired physical properties.
• the usual pigment finish is a thermal aftertreatment, whereby a better formation of crystals is achieved by heating the pigment raw suspension or the salt-free washed, isolated and pasted pigment press cake in water and / or organic solvents.
• the fine grain fraction which is particularly responsible for the tendency of the pigments to agglomerate, is reduced and consequently a narrower grain size distribution is achieved.
• organic solvents particularly poorly soluble pigments are post-treated at temperatures from 80 to 150 ° C. For example, alcohols, glacial acetic acid, chlorobenzene, o-dichlorobenzene and dimethylformamide are used for this.
• the finishing processes that have been customary up to now are expensive in terms of equipment and energy, since they are often heated under pressure and the solvent is distilled off. There If organic solvents are mostly flammable, appropriate measures must be taken to ensure plant safety.
• the object of the present invention was to provide a suitable finishing process for organic pigments which is superior to the solvent finish which has been customary to date in terms of safety, environmental compatibility and use of resources.
• ionic liquids Organic salts that are liquid at temperatures below 100 ° C are called ionic liquids.
• ionic liquids are a suitable finishing medium for organic pigments.
• the present invention therefore relates to a method for
• the procedure is such that one after the
• a water-moist or solvent-moist raw pigment e.g. a filter cake or press cake can be used.
• the aftertreatment according to the invention is expediently carried out in a heatable reaction vessel with a stirring device.
• the ionic liquid can be added to the raw pigment in liquid or solid form and then the mixture can be brought to a temperature above the melting point of the ionic liquid by heating.
• the preferred The temperature range for the aftertreatment is between 25 ° C and 280 ° C, preferably between 80 and 200 ° C.
• the ionic liquid is expediently used in an amount (ionic liquid: pigment) of (0.5: 1) to (30: 1), preferably (1: 1) to (20: 1).
• the water or the solvent can remain in the mixture during the aftertreatment or can be removed from the mixture by distillation before or during the aftertreatment.
• water or organic solvents e.g. Hydrocarbons, alcohols, ethers, amines, carboxylic acids, carboxylic acid esters or amides, e.g. N-methyl pyrrolidone to add.
• the proportion of water or organic solvent can be in the range from 1 to 90% by weight, preferably in the range from 5 to 50% by weight, based on the total amount of the pigment suspension.
• the duration of the aftertreatment can vary within wide limits; 10 minutes to 10 hours, preferably 30 minutes to 5 hours, are advisable.
• the pigment is then separated from the ionic liquid by filtration. It may be advantageous to add water or an organic solvent e.g. from the group of hydrocarbons, alcohols, ethers, amines, carboxylic acids, carboxylic acid esters or amides, such as e.g.
• the ionic liquid can be recovered from the filtrate by extraction or by distilling off water and / or organic solvents and used again for the aftertreatment of pigments.
• the ionic liquid can be miscible or immiscible with water.
• [B] ⁇ is an organic or an inorganic anion selected from the group consisting of halide, borate, phosphate, phosphonate, antimonate, arsenate, zincate, cuprate, aluminate, carbonate, alkyl carbonate, alkyl sulfonate, sulfate, alkyl sulfate, alkyl ether sulfate, amide, imide , Carbanion and anionic metal complex; [A] + is a cation selected from
• imidazole core can be substituted with at least one radical from the group CrC 6 alkyl, Ci-Ce alkoxy, CrC 6 aminoalkyl, C 6 -Ci 2 aryl or C 6 -C 2 aryl d-Ce alkyl,
• pyridine core can be substituted with at least one radical from the group -C-C 6 alkyl, Ci-Ce-alkoxy, Ci-Ce-aminoalkyl, C 6 -C ⁇ 2 aryl or C 6 -C 12 aryl- CrC ⁇ -alkyl,
• pyrazole nucleus can be substituted with at least one radical from the group CrC 6 -alkyl, -C-C 6 -alkoxy, Ci-Ce-aminoalkyl, C 6 -C ⁇ 2 -aryl or C 6 -C ⁇ 2 -aryl- d -ce-alkyl,
• triazole nucleus may be substituted with at least one radical from the group Ci-Ce-alkyl, CrC 6 -alkoxy, C 6 aminoalkyl, C 6 -C ⁇ 2 -aryl or C 6 -C -C ⁇ 2 -aryl 6 alkyl,
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently selected from the group:
• Aryl groups with 6 to 12 carbon atoms in the aryl radical, which can optionally be substituted with at least one d-C6-alkyl group and / or a halogen atom.
• Preferred anions of the ionic liquids are chloride (Cl ⁇ ), bromide (Br “ ), tetrafluoroborate ([BF 4 ] “ ), tetrachloroborate ([BCI 4 ] “ ), tetracyanoborate ([B (CN) 4 ] “ ), bis [ oxolato (2 -)] borate ([B (OOC-COO) 2 ] " ), bis [malonato (2 -)] borate
• Preferred organic cations of the ionic liquids are tetramethylammonium, tetraethylammonium, tetrabutylammonium, trioctylmethylammonium, 1, 1-dimethylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium, 1-butyl-1-methylpyrrolidinium , 1-butyl-1-ethyl-pyrrolidinium, 1-hexyl-1-methyl-pyrrolidinium, 1-octyl-1-methyl-pyrrolidinium, 1, 1-dipropyl-pyrrolidinium, 1, 1-dibutyl-pyrrolidinium, 1, 1 -Dihexylpyrrolidinium, tetrabutyl-phosphonium, trihexyl- (tetradecyl) -phosphonium, triisobutyl-methyl-phosphonium, benzyl-triphenyl-phosphonium, 1-methyl-imidazolium
• C.I. come in particular as azo pigments Pigment Yellow 16, 32, 83, 97, 120, 151, 154, 155, 175, 180, 181, 191, 194, 213, Pigment Orange 34, 36, 38, 62, 72, 74, Pigment Red 53: 2, 112, 122, 137, 144, 170, 171, 175, 176, 185, 187, 188, 208, 214, 242, 247, 253; Pigment violet 32; Pigment Brown 25 into consideration.
• Polycyclic pigments can e.g. Isoindolinone, isoindoline, anthanthrone, thioindigo, quinophthalone, anthraquinone, dioxazine, phthalocyanine, quinacridone, perylene, perinone, diketopyrrolopyrrole, thiazine indigo and azomethine pigments, in particular pigment Violet 19, 23 , Pigment Blue 15, Pigment Green 7, 36, 37, Pigment Red 122, 179, 202, 254, Pigment Yellow 139.
• the aftertreatment according to the invention can replace the previously customary aqueous or solvent finish.
• some pigments can surprisingly have other physical properties
• a P.R. 170 of the ⁇ phase or the ⁇ phase or a mixture of the ⁇ phase and the ⁇ phase For example, from raw P.R. 170 of the ⁇ phase by the post-treatment according to the invention a P.R. 170 of the ⁇ phase or the ⁇ phase or a mixture of the ⁇ phase and the ⁇ phase.
• a PY 213 of the ⁇ phase is formed from raw PY 213 of the ⁇ phase by the aftertreatment according to the invention.
• the coloristic properties of the pigment samples obtained in the alkyd-melamine stove enamel AM 5 were determined by comparative measurements; the untreated samples served as reference.
• the brightening was assessed by colorimetric measurement of the CIELAB system according to DIN 6174; was measured on a PCM device from Gardner, the mean value being formed from three individual values.
• the full tone was assessed visually under a matching lamp in accordance with ASTM D1729 with daylight (CIE D65).
• the crystal modification of the pigments obtained was determined by X-ray powder diffractometry.
• Example 2 The procedure was as in Example 1, but instead of the dried raw pigment, 136 g of crude pigment P.R. 170 were used as a water-moist press cake (alpha phase). The mixture of crude pigment, ECOENG 41 M and water was heated to 110 ° C. within 10 minutes and
• Example 7 Finish of PR 170 (dry pigment) with CYPHOS 3653
• the alpha phase of PR 170 is understood to mean the crystal modification which is characterized by the following characteristic lines in the X-ray powder diagram (Cu-K ⁇ radiation, 2 ⁇ values in degrees): 7.6 (strong), 25.7 (strong), 5.2, 8.2 , 11.7, 13.5, 15.9, 18.9, 23.5 (all moderately strong).
• the beta phase is the crystal modification of PR 170 that is characterized by the following characteristic lines in the X-ray powder diagram: 25.5 (strong), 7.1, 8.2, 11.3, 12.8, 15.1, 17.9 (all weak).
• the gamma phase is characterized by the following lines: 25.7 (strong), 7.3, 11.3, 12.9, 15.4, 18.2 (all moderately strong). All line positions of all modifications of all pigments are subject to an inaccuracy of ⁇ 0.2 °.
• Example 8 Finish of P.Y. 213 (dry pigment) with ECOENG 41 M.
• the pigment resulting from the aftertreatment is distinguished from the untreated form (brown color) by a brilliant yellow color.
• Example 9 Finish of copper phthalocyanine (raw blue) with ECOENG 41 M.
• Example 2 The procedure was as in Example 1, but 25 g of copper phthalocyanine (raw blue) were used instead of P.R. 170 used and the mixture heated to 130 ° C for 3 hours. 24.4 g of copper phthalocyanine are obtained in the beta phase.
• the pigment resulting from the after-treatment is distinguished from the untreated form (cloudy blue) by a brilliant greenish-blue color.
• Example 10 Finish of copper phthalocyanine (raw blue) with CYPHOS 3653

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Optical Filters (AREA)

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• 2004
  • 2004-05-14 DE DE102004024000A patent/DE102004024000A1/de not_active Withdrawn
• 2005
  • 2005-04-28 WO PCT/EP2005/004541 patent/WO2005111151A1/de not_active Ceased
  • 2005-04-28 US US11/596,640 patent/US20070215007A1/en not_active Abandoned
  • 2005-04-28 JP JP2007511964A patent/JP4624408B2/ja not_active Expired - Fee Related
  • 2005-04-28 EP EP05738472A patent/EP1749063B1/de not_active Expired - Lifetime
  • 2005-04-28 DE DE502005010653T patent/DE502005010653D1/de not_active Expired - Lifetime

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