WO2004009688A2 - Use of solid pigment preparations for colouring plastics - Google Patents

Use of solid pigment preparations for colouring plastics Download PDF

Info

Publication number
WO2004009688A2
WO2004009688A2 PCT/EP2003/007591 EP0307591W WO2004009688A2 WO 2004009688 A2 WO2004009688 A2 WO 2004009688A2 EP 0307591 W EP0307591 W EP 0307591W WO 2004009688 A2 WO2004009688 A2 WO 2004009688A2
Authority
WO
WIPO (PCT)
Prior art keywords
pigment
plastics
pigments
pigment preparations
weight
Prior art date
Application number
PCT/EP2003/007591
Other languages
German (de)
French (fr)
Other versions
WO2004009688A3 (en
Inventor
Andreas Stohr
Hansulrich Reisacher
Juan Antonio Gonzalez Gomez
Heinrich Schmeisser
Uemit Z. Hancer
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2003250052A priority Critical patent/AU2003250052A1/en
Publication of WO2004009688A2 publication Critical patent/WO2004009688A2/en
Publication of WO2004009688A3 publication Critical patent/WO2004009688A3/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02Polyalkylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041Optical brightening agents, organic pigments
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41Compounds containing sulfur bound to oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/58Ethylene oxide or propylene oxide copolymers, e.g. pluronics

Definitions

  • the present invention relates to the use of solid pigment preparations, which are essential components
  • the invention further relates to a method for coloring plastics.
  • Powder pigments are usually used to color plastics.
  • the complete dispersion of the pigments in the plastic is a prerequisite for the development of maximum color strength and coloring effect.
  • Such a dispersion requires appropriate know-how and a high input of shear energy and is therefore expensive.
  • the plastics processor does not have this know-how and the necessary complex and expensive dispersing devices, the colored plastics often have so-called pigment specks, i.e. pigment agglomerates that are not completely dispersed, on ,, are difficult to spin and / or have high pressure filter values.
  • a masterbatch is a usually solid, concentrated pigment preparation in a meltable plastic matrix that is solid at room temperature, in which the powdered pigment is dispersed and thus finely distributed, i.e. the energy required to disperse the powder pigment was already used in the manufacture of the
  • the object of the invention was to provide pigment preparations with which plastics of the most varied types can advantageously be colored.
  • a process for coloring plastics was also found, which is characterized in that these pigment preparations are incorporated into the plastics by extrusion, rolling, kneading or grinding.
  • the pigment preparations to be used according to the invention contain at least one pigment as component (A) and at least one nonionic surface-active additive based on polyethers or at least one anionic surface-active agent based on the acidic phosphoric, phosphonic, sulfuric acid as component (B) - Or sulfonic acid esters of the polyethers or their salts (B) or a mixture of these non-ionic and anionic surface-active additives.
  • Organic or inorganic pigments may be present as component (A) in the pigment preparations to be used according to the invention.
  • the pigment preparations can of course also contain mixtures of different organic or different inorganic pigments or mixtures of organic and inorganic pigments.
  • the pigments are in finely divided form. Accordingly, the pigments usually have average particle sizes of 0.1 to 5 ⁇ m, in particular 0.1 to 3. ⁇ m and especially 0.1 to 1 ⁇ m.
  • the organic pigments are usually organic colored and black pigments. Inorganic pigments can also be color pigments (colored, black and white pigments) as well as gloss pigments and the inorganic pigments usually used as fillers.
  • Disazo condensation pigments C.I. Pigment Yellow 93, 95 and 128;
  • Anthraquinone pigments C.I. Pigment Yellow 147, 177 and 199;
  • Anthrapyrimidine pigments C.I. Pigment yellow 108;
  • Isoindoline pigments C.I. Pigments Orange 61 and 69;
  • Isoindolinone pigments C.I. Pigment Yellow 109, 110 and 173;
  • Phthalocyanine Pigments CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; CI Pigment Green 7 and 36;
  • Triarylcarbonium pigments C.I. Pigment Blue 1, 61 and 62;
  • Suitable inorganic color pigments are e.g.
  • Iron-manganese black spinel black (C.I. Pigment Black 27); Carbon black (C.I. Pigment Black 7);
  • chromium oxide chromium oxide hydrate green
  • Chrome green C.I. Pigment Green 48
  • Cobalt green C.I. Pigment Green 50
  • Ultramarine green chromium oxide, chromium oxide hydrate green
  • Chrome green C.I. Pigment Green 48
  • Cobalt green C.I. Pigment Green 50
  • Ultramarine green chromium oxide, chromium oxide hydrate green
  • Chrome green C.I. Pigment Green 48
  • Cobalt green C.I. Pigment Green 50
  • Ultramarine green Ultramarine green
  • Cobalt blue (CI. Pigment Blue 28 and 36; CI Pigment Blue 72); Ultramarine blue; Manganese blue; Ultramarine violet; Cobalt and manganese violet;
  • Iron oxide red C.I. Pigment Red 101
  • Cadmium sulfoselenide C.I. Pigment Red
  • Iron oxide brown (C.I. Pigment Brown 6 and
  • Cerium sulfide Cerium sulfide (C.I. Pigment Orange 75); Iron oxide yellow (C.I. Pigment Yellow 42); Nickel titanium yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); Chromium titanium yellow; Spinel phases (C.I. Pigment Yellow 119); Cadmium sulfide and cadmium zinc sulfide (C.I. Pigment Yellow 37 and 35); Chrome yellow (C.I. Pigment Yellow 34); Bismuth vanadate (C.I. Pigment Yellow 184).
  • inorganic pigments commonly used as fillers are transparent silicon dioxide, quartz powder, aluminum oxide, aluminum hydroxide, natural mica, natural and precipitated chalk and barium sulfate.
  • the luster pigments are single-phase or multi-phase platelet-shaped pigments whose play of colors is • characterized by the interplay of interference, reflection and absorption phenomena. Examples include aluminum flakes and aluminum, iron oxide and mica flakes coated one or more times, in particular coated with metal oxides.
  • the solid pigment preparations to be used according to the invention contain, as component (B), surface-active additives based on polyethers, which can be modified nonionically or anionically. Different nonionic and different anionic additives as well as mixtures of nonionic and anionic additives can be contained.
  • Anionic surface-active additives are the acidic phosphoric acid, phosphonic acid, sulfuric acid and / or sulfonic acid esters of the polyethers and / or their salts.
  • the nonionic surface-active additives based on polyether are, in particular, polyalkylene oxides or reaction products of alkylene oxides with alcohols, amines, aliphatic carboxylic acids or aliphatic carboxylic acid amides.
  • alkylene oxide should also be understood to mean aryl-substituted alkylene oxide, in particular phenyl-substituted ethylene oxide.
  • CC alkylene oxides and phenyl-substituted C 2 -C alkylene oxides such as polyethylene oxides, polypropylene oxides and poly (phenyl ethylene oxides), alkylene oxide block copolymers, but also random copolymers of these alkylene oxides, are particularly suitable as component (B).
  • Block copolymers which have polypropylene oxide and polyethylene oxide blocks or else poly (phenylethylene oxide) and polyethylene oxide blocks are very particularly suitable.
  • they can be obtained by polyaddition of the alkylene oxides to starter compounds, such as saturated or unsaturated aliphatic and aromatic alcohols, saturated or unsaturated aliphatic and aromatic amines, saturated or unsaturated aliphatic carboxylic acids and carboxamides.
  • starter compounds such as saturated or unsaturated aliphatic and aromatic alcohols, saturated or unsaturated aliphatic and aromatic amines, saturated or unsaturated aliphatic carboxylic acids and carboxamides.
  • these starter compounds can first be reacted with ethylene oxide and then with propylene oxide or preferably first with propylene oxide and then with ethylene oxide.
  • 1 to 300 ol, preferably 3 to 150 ol, of alkylene oxide are used per mol of starter molecule.
  • Suitable aliphatic alcohols generally contain 6 to 26 carbon atoms, preferably 8 to 18 carbon atoms, and can be unbranched, branched or cyclic. Examples include octanol, nonanol, decanol, isodecanol, undecanol, dodecanol, 2-butyloctanol, tridecanol, isotridecanol, tetra-decanol, pentadecanol, hexadecanol, 2-hexyl ecanol, heptadecanol, octadecanol, 2-heptylundecanol, 2-octyldecanol and 2-octyldecanol.
  • saturated and unsaturated fatty alcohols which are obtained from natural raw materials through fat splitting and reduction, and the synthetic fatty alcohols from oxosynthesis.
  • the alkylene oxide adducts with these alcohols usually have average molecular weights M n of 200 to 5000, especially 400 to 2000.
  • aromatic alcohols include, in addition to - and ß-naphthol and their C 1 -C 4 -alkyl derivatives, especially phenol and its C ⁇ -Ci 2 alkyl derivatives, such as hexylphenol, heptylphenol, octylphenol, nonylphenol, isononylphenol, undecylphenol, dodecylphenol, Di- and tributylphenol and dinonylphenol 10 called.
  • Suitable aliphatic amines correspond to the aliphatic alcohols listed above.
  • the saturated and unsaturated fatty amines which preferably have 14 to 15 20 C atoms, are of particular importance.
  • Aniline and benzidine and their derivatives may be mentioned as aromatic amines.
  • Suitable aliphatic carboxylic acids are, in particular, saturated and unsaturated fatty acids, which preferably contain 14 to 20 C atoms, and hydrogenated, partially hydrogenated and unhydrogenated resin acids and also polyvalent carboxylic acids, e.g. Dicarboxylic acids such as maleic acid.
  • Suitable carboxamides are derived from these carboxylic acids 25.
  • the alkylene oxide adducts with these monohydric amines and alcohols are of particular interest.
  • Preferred at least bifunctional amines are di- to pentavalent amines, which in particular have the formula H 2 N- (R-NR 1 ) n -H (R: C 2 -C 6 alkylene; R 1 : hydrogen or Ci-C ⁇ - Alkyl; n: 1 to 5) correspond.
  • Examples include: ethylenediamine,
  • the amines are preferably first reacted with propylene oxide and then with ethylene oxide.
  • the ethylene oxide content of the block copolymers is usually about 10 to 90 5% by weight.
  • the block copolymers based on polyvalent amines generally have average molecular weights M n of 1,000 to 40,000, preferably 1,500 to 30,000.
  • Dihydric to pentavalent alcohols are preferred as at least bifunctional alcohols.
  • Examples include C 2 -C 6 alkylene glycols and the corresponding di- and polyalkylene glycols, such as ethylene glycol, propylene glycol-1, 2 and -1.3, butylene glycol-1, 2 and -1.4, hexylene glycol-1,6, Dipropylene glycol and polyethylene glycol, glycerol and pentaerythritol and bisphenol-A are mentioned, ethylene glycol and polyethylene glycol being particularly preferred and propylene glycol and dipropylene glycol being very particularly preferred.
  • Particularly preferred alkylene oxide adducts with at least bifunctional alcohols have a central polypropylene oxide block, that is to say they start from a propylene glycol or polypropylene glycol which is first reacted with further propylene oxide and then with ethylene oxide.
  • the ethylene oxide content of the block copolymers is usually from 10 to 90% by weight.
  • the block copolymers based on polyhydric alcohols generally have average molecular weights M n of 1000 to 20,000, preferably 1000 to 15,000.
  • alkylene oxide block copolymers are known and commercially available e.g. available under the names Tetronic and Pluronic (BASF).
  • the anionic surface-active additives (B) are the sulfonates, sulfates, phosphonates and phosphates of the polyethers.
  • the polyethers can be converted into the phosphoric acid monoesters or diesters and phosphonic acid esters or the sulfuric acid monoesters and sulfonic acid esters by reaction with phosphoric acid, phosphorus pentoxide and phosphonic acid or sulfuric acid and sulfonic acid.
  • These acidic esters are preferably in the form of water-soluble salts, especially as alkali metal salts, especially sodium salts, and ammonium salts, but they can also be used in the form of the free acids.
  • Preferred phosphates and phosphonates are derived primarily from alkoxylated, in particular ethoxylated, fatty and oxo alcohols, alkylphenols, fatty amines, fatty acids and resin acids, preferred sulfates and sulfonates are based in particular on alkoxylated, especially ethoxylated, fatty alcohols, alkyl alcohols. phenols and amines, including polyvalent amines, such as hexamethylene diamine.
  • anionic surface active additives are known and commercially available for example under the name Nekal ® (BASF), Tamol ® (BASF), Cro dafos ® (Croda), Rhodafac ® (Rhodia), Mapho ⁇ ® (BASF), Texapon ® (co gnis), Empicol ® (Albright & Wilson), Matexil ® (ICI), Soprophor ® (Rhodia) and Lutensit ® (BASF).
  • Nekal ® BASF
  • Tamol ® BASF
  • Cro dafos ® Cro dafos ®
  • Rhodafac ® Rhodia
  • Mapho ⁇ ® BASF
  • Texapon ® co gnis
  • Empicol ® Albright & Wilson
  • Matexil ® ICI
  • Soprophor ® Rosit ®
  • Lutensit ® BASF
  • the pigment preparations to be used according to the invention contain 60 to 90% by weight, preferably 70 to 85% by weight, of the component
  • component (B) (A) and 10 to 40% by weight, preferably 15 to 30% by weight, of component (B).
  • the pigment preparations to be used in accordance with the invention can advantageously be prepared by initially pigmenting (A) in aqueous, at least part of, the additive (s)
  • (B) containing suspension is subjected to wet comminution and the suspension is then dried, optionally after addition of the remaining amount of additive (B).
  • the pigment (A) can be used as a dry powder or in the form of a press cake.
  • the pigment (A) used is preferably a finished product, i.e. the primary grain size of the pigment is already set to the value desired for the application.
  • This pigment finish is particularly recommended for organic pigments, since the raw material obtained during pigment synthesis is generally not suitable for the application.
  • the primary grain size can also be set during pigment synthesis, so that the pigment suspensions obtained can be used directly for the preparation of the pigment preparations to be used according to the invention.
  • the finished pigment (A) usually reaglomerates again during drying or on the filter unit, it is used to adjust the above-mentioned average particle sizes in aqueous suspension of continuous or discontinuous wet comminution, for example a stirrer, dissolver or high-pressure homogenization or grinding, in particular in an agitator ball mill.
  • At least one part of the additive (B) contained in the finished pigment preparation should be present during the wet comminution, preferably the entire amount of additive (B) is added before the wet comminution.
  • the particle size of the pigment preparations according to the invention can be controlled in a targeted manner.
  • fine-particle granules with average grain sizes of 50 to 5000 m, in particular 100 to 1000 ⁇ m, can be obtained.
  • Spray drying usually gives granules with average grain sizes ⁇ 20 ⁇ m.
  • Finely divided preparations can be obtained by drying in a paddle dryer and by evaporation with subsequent grinding.
  • the pigment preparations used according to the invention are preferably in granule form, the coarse-particle granules being particularly preferred.
  • the spray granulation is preferably carried out in a spray tower with a one-off nozzle.
  • the suspension is sprayed here in the form of larger drops, the water evaporating.
  • Da ⁇ or the additives (B) melt at the drying temperatures and thus lead to the formation of largely spherical granules with a particularly smooth surface (BET values of generally ⁇ 15 m 2 / g, in particular ⁇ 10 m 2 / g), which is preferred according to the invention.
  • the gas inlet temperature in the spray tower is generally from 180 to 300 ° C., preferably from 150 to 300 ° C.
  • the gas outlet temperature is generally 70 to 150 ° C., preferably 70 to 130 ° C.
  • the residual moisture of the pigment granules obtained is generally ⁇ 2% by weight.
  • the pigment preparations can advantageously be used for coloring all kinds of plastics.
  • plastic classes and types are mentioned as examples: modified natural substances:
  • Duropla ⁇ te e.g. Ca ⁇ ein-Kunst ⁇ toffe
  • Thermoplastics e.g. Cellulose nitrate, cellulose acetate, mixed cellulose esters and cellulose ether;
  • Duropla ⁇ te for example, phenol resin, urea resin, thiourea, melamine resin, unsaturated polyester resin, allyl resin, silicone, Poly I 'mid and polybenzimidazole;
  • Thermoplastics for example polyamide, polycarbonate, polyester, polyphenylene oxide, polysulfone and polyvinyl acetal;
  • thermoplastics e.g. Polyolefins, such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene, ionomers, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, polyacrylonitrile, polystyrene, polyacetal ', fluoroplastics, polyvinyl alcohol, polyvinyl acetate and polyvinyl p-xylylene and copolymers, such as ethylene / vinyl acetate copolymers, styrene / acrylonitrile copolymers, acrylonitrile / butadiene / styrene copolymers, polyethylene glycol terephthalate and polybutylene glycol terephthalate;
  • Polyolefins such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene
  • ionomers polyvinyl chloride,
  • Duropla ⁇ te e.g. Epoxy resin and cross-linked polyurethane
  • Thermoplastics e.g. linear polyurethanes and chlorinated polyethers.
  • the solid pigment preparations to be used according to the invention are notable for their particularly easy dispersibility. This also applies in particular to the pigment preparations in granular form which are preferably to be used according to the invention and which are distinguished by the following additional advantageous properties: excellent abrasion resistance, low tendency to compact or clump, uniform particle size distribution, good debris, free-flowing and metering capacity and freedom from dust in handling and application.
  • the plastics can advantageously with little energy input, e.g. by extruding them together (preferably using a single or twin screw extruder), rolling, kneading or grinding, with the pigment preparations. They can exist as plastic masses or melts and can be processed into plastic moldings, foils and fibers.
  • the solid pigment preparations to be used according to the invention are distinguished by generally advantageous application properties, especially good color properties, in particular particularly high color strength and brilliance, and the good rheological properties of the plastics colored with them, in particular low pressure filter values (high filter service life) and good spinnability.
  • plastics can be used for direct coloring of plastics as well as for coloring masterbatches and compounds.
  • direct plastic coloring they are generally used in quantities of 0.1 to 5% by weight, based on the plastic to be colored.
  • coloring masterbatches up to 70% by weight pigment preparation, based on the plastic to be colored, can be used , are used.
  • the pigment granules were produced by a
  • B1 block copolymer based on ethylenediamine / propylene oxide / ethylene oxide with an ethylene oxide content of 40% by weight and an average molecular weight M n of 12,000.
  • B2 block copolymer based on ethylene oxide / propylene oxide / ethylene oxide with an ethylene oxide content of 50% by weight and an average molecular weight M n of 6500.
  • B3 block copolymer based on ethylene oxide / propylene oxide / ethylene oxide with an ethylene oxide content of 10% by weight and an average molecular weight M n of 3500.
  • the dispersion hardness was determined in white lightening in soft PVC.
  • the PVC sheets investigated were produced as described above and measured colorimetrically. The calculation of the dispersion hardness (DH) was made from those obtained during the measurement
  • the filter test was carried out as follows: after installing the filter cassette with the filter pack, there was a wait until the thermal equilibrium was reached.
  • the filter package was used so that the fine sieve (number of warp threads in 3.5 mm: 42; number of weft threads in 3.5 mm: 17; number of stitches: 10870 / cm 2 ; absolute filter fineness: 33-37 ⁇ m) of the material flow was reached.
  • the system was then started up using unpigaynetem polypropylene, the developing before the filter 'pressure (initial pressure Pl) was determined. Subsequently, the measurement was also conveyed through the filter package while measuring the pressure. The pressure upstream of the filter may increase due to any particles present. The. The highest pressure reached in this phase is the final pressure P2.
  • the pressure filter values were calculated from the pressure values using the following formula (DFW values ⁇ 2.0 bar / g are considered good):

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention relates to the use of solid pigment preparations for colouring plastics, said preparations containing the following as essential constituents: (A) between 60 and 90 wt. % of at least one pigment; and (B) between 10 and 40 wt % of at least one surface-active additive from the group of non-ionic polyethers, their acidic phosphoric acid esters, phosphonic acid esters, sulphuric acid esters and/or sulphonic acid esters and their salts.

Description

Verwendung von festen PigmentZubereitungen zur Einfärbung von KunststoffenUse of solid pigment preparations for coloring plastics
Beschreibungdescription
Die vorliegende Erfindung betrifft die Verwendung von festen Pigmentzubereitungen, die als wesentliche BestandteileThe present invention relates to the use of solid pigment preparations, which are essential components
(A) 60 bis 90 Gew.-% mindestens eines Pigments und(A) 60 to 90% by weight of at least one pigment and
(B) 10 bis 40 Gew.-% mindestens eines oberflächenaktiven Additivs aus der Gruppe der nichtionisehen Polyether und ihrer sauren Phosphorsäure-, Phosphonsäure-, Schwefelsäure- und/oder Sulfonsäureester und deren Salzen(B) 10 to 40% by weight of at least one surface-active additive from the group of the nonionic polyethers and their acidic phosphoric, phosphonic, sulfuric and / or sulfonic esters and their salts
enthalten, zur Einfärbung von Kunststoffen.included, for coloring plastics.
Weiterhin- betrifft die Erfindung ein Verfahren zur Einfärbung von Kunststoffen.The invention further relates to a method for coloring plastics.
Zur Einfärbung von Kunststoffen werden üblicherweise Pulverpigmente eingesetzt. Dabei ist die vollständige Dispergierung der Pigmente im Kunststoff Voraussetzung für die Entwicklung von ma- ximaler Farbstärke und Färbewirkung. Eine solche Dispergierung erfordert ein entsprechendes Know-how und einen hohen Eintrag an Scherenergie und ist daher kostspielig. Wenn der Kunststoffver- arbeiter nicht über dieses Know-how sowie die erforderlichen aufwendigen und teuren Dispergiergeräte verfügt, weisen die einge- färbten Kunststoffe oftmals sogenannte Pigmentstippen, d.h. nicht ausdispergierte Pigmentagglomerate, auf,, sind schlecht verspinn- bar und/oder besitzen hohe Druckfilterwerte.Powder pigments are usually used to color plastics. The complete dispersion of the pigments in the plastic is a prerequisite for the development of maximum color strength and coloring effect. Such a dispersion requires appropriate know-how and a high input of shear energy and is therefore expensive. If the plastics processor does not have this know-how and the necessary complex and expensive dispersing devices, the colored plastics often have so-called pigment specks, i.e. pigment agglomerates that are not completely dispersed, on ,, are difficult to spin and / or have high pressure filter values.
Viele Kunststoffverarbeiter greifen daher für die Einfärbung von Kunststoffen auf sogenannte Masterbatches zurück. Ein Masterbatch ist eine üblicherweise feste, konzentrierte Pigmentpräparation in einer schmelzbaren, bei Raumtemperatur festen Kunststoffmatrix, in der das pulverförmige Pigment ausdispergiert und damit feinverteilt vorliegt, d.h. die zur Dispergierung des Pulverpigments erforderliche Energie wurde bereits bei der Herstellung desMany plastics processors therefore use so-called masterbatches for coloring plastics. A masterbatch is a usually solid, concentrated pigment preparation in a meltable plastic matrix that is solid at room temperature, in which the powdered pigment is dispersed and thus finely distributed, i.e. the energy required to disperse the powder pigment was already used in the manufacture of the
Masterbatches aufgebracht. Mit Hilfe dieser Masterbatches können die Kunststoffverarbeiter die Kunststoffe ohne großen Energieaufwand einfärben und erhalten gleichzeitig hinsichtlich Farbstärke und Farbton konstantere Färbeergebnisse. Aus der EP-A-1 081 195 sind granuläre Pigmentzubereitungen für die Einfärbung von Kunststoffen bekannt, die nichtionische Poly- ethylenwachse als Additive enthalten. Diese PigmentZubereitungen werden durch Inkontaktbringen der Pigmente mit den Wachsen beim Lösungsmittelfinish und Sprühtrocknung hergestellt. Dieses Herstellungsverfahren ist jedoch nur für organische Pigmente anwendbar, die in organischen Lösungsmitteln gefinisht werden.Masterbatches applied. With the help of these masterbatches, the plastics processor can color the plastics without much energy consumption and at the same time obtain more consistent coloring results with regard to color strength and shade. From EP-A-1 081 195 granular pigment preparations for coloring plastics are known which contain nonionic polyethylene waxes as additives. These pigment preparations are produced by bringing the pigments into contact with the waxes during solvent finishing and spray drying. However, this manufacturing process is only applicable to organic pigments that are finished in organic solvents.
Weiterhin ist in den älteren deutschen Patentanmeldungen 10204304.3 sowie 10204583.6, 10227657.9 und 10228199.8 der Einsatz von festen Pigmentzubereitungen, die nichtionische oberflächenaktive Additive auf der Basis von Polyethern bzw. Mischungen dieser Additive mit anionischen oberflächenaktiven Additiven auf Basis entsprechend modifizierter Polyether enthalten, beschrieben.Furthermore, the older German patent applications 10204304.3 and 10204583.6, 10227657.9 and 10228199.8 describe the use of solid pigment preparations which contain nonionic surface-active additives based on polyethers or mixtures of these additives with anionic surface-active additives based on appropriately modified polyethers.
Der Erfindung lag die Aufgabe zugrunde, Pigmentzubereitungen bereitzustellen, mit denen Kunststoffe verschiedenster Art vorteilhaft eingefärbt werden können.The object of the invention was to provide pigment preparations with which plastics of the most varied types can advantageously be colored.
Demgemäß wurde die Verwendung von festen PigmentZubereitungen, die als wesentliche BestandteileAccordingly, the use of solid pigment preparations, which are essential components
(A) 60 bis 90 Gew.-% mindestens eines Pigments und(A) 60 to 90% by weight of at least one pigment and
(B) 10 bis 40 Gew.-% mindestens eines oberflächenaktiven Additivs aus der Gruppe der nichtionischen Polyether und ihrer sauren Phosphorsäure-, Phosphonsäure- , Schwefelsäure- und/oder(B) 10 to 40% by weight of at least one surface-active additive from the group of the nonionic polyethers and their acidic phosphoric, phosphonic, sulfuric and / or
Sulfonsäureester und deren SalzenSulfonic acid esters and their salts
enthalten, zur Einfärbung von Kunststoffen gefunden.included, found for coloring plastics.
Weiterhin wurde ein Verfahren zur Einfärbung von Kunststoffen gefunden, welches dadurch gekennzeichnet ist, daß man diese Pigmentzubereitungen durch Extrudieren, Walzen, Kneten oder Mahlen in die Kunststoffe einarbeitet.A process for coloring plastics was also found, which is characterized in that these pigment preparations are incorporated into the plastics by extrusion, rolling, kneading or grinding.
Die erfindungsgemäß zu verwendenden Pigmentzubereitungen enthalten als Komponente (A) mindestens ein Pigment sowie als Kompo- nente (B) mindestens ein nichtionisches oberflächenaktives Additiv auf der Basis von Polyethern oder mindestens ein anionisches oberflächenaktives Mittel auf der Basis der sauren Phosphorsäure-, Phosphonsäure-, Schwefelsäure- oder Sulfonsäureester der Polyether oder deren Salzen (B) oder eine Mischung dieser nicht- ionischen und anionischen oberflächenaktiven Additive. Als Komponente (A) können in den erfindungsgemäß zu verwendenden Pigmentzubereitungen organische oder anorganische Pigmente enthalten sein. Selbstverständlich können die PigmentZubereitungen auch Mischungen verschiedener organischer oder verschiedener an- organischer Pigmente oder Mischungen von organischen und anorganischen Pigmenten enthalten.The pigment preparations to be used according to the invention contain at least one pigment as component (A) and at least one nonionic surface-active additive based on polyethers or at least one anionic surface-active agent based on the acidic phosphoric, phosphonic, sulfuric acid as component (B) - Or sulfonic acid esters of the polyethers or their salts (B) or a mixture of these non-ionic and anionic surface-active additives. Organic or inorganic pigments may be present as component (A) in the pigment preparations to be used according to the invention. The pigment preparations can of course also contain mixtures of different organic or different inorganic pigments or mixtures of organic and inorganic pigments.
Die Pigmente liegen in feinteiliger Form vor. Die Pigmente haben dementsprechend üblicherweise mittlere Teilchengrößen von 0,1 bis 5 um, insbesondere 0,1 bis 3. μ und vor allem 0,1 bis 1 um. Bei den organischen Pigmenten handelt es sich üblicherweise um organische Bunt- und Schwarzpigmente. Anorganische Pigmente können ebenfalls Farbpigmente (Bunt-, Schwarz- und Weißpigmente) sowie Glanzpigmente und die üblicherweise als Füllstoffe eingesetz- ten anorganischen Pigmente sein.The pigments are in finely divided form. Accordingly, the pigments usually have average particle sizes of 0.1 to 5 μm, in particular 0.1 to 3. μm and especially 0.1 to 1 μm. The organic pigments are usually organic colored and black pigments. Inorganic pigments can also be color pigments (colored, black and white pigments) as well as gloss pigments and the inorganic pigments usually used as fillers.
Im folgenden seien als Beispiele für geeignete organische Farbpigmente genannt :The following are examples of suitable organic color pigments:
- Monoazopigmente: C.I. Pigment Brown 25;- Monoazo pigments: C.I. Pigment brown 25;
C.I. Pigment Orange 5, 13, 36, 38, 64 und 67;C.I. Pigment Orange 5, 13, 36, 38, 64 and 67;
C.I. Pigment Red 1, 2, 3, 4, 5, 8, 9,C.I. Pigment Red 1, 2, 3, 4, 5, 8, 9,
12, 17, 22, 23, 31, 48:1, 48:2, 48:3,12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3,
48:4, 49, 49:1, 51:1, 52:1, 52:2, 53,48: 4, 49, 49: 1, 51: 1, 52: 1, 52: 2, 53,
53:1, 53:3, 57:1, 58:2, 58:4, 63, 112,53: 1, 53: 3, 57: 1, 58: 2, 58: 4, 63, 112,
146, 148, 170, 175, 184, 185, 187,146, 148, 170, 175, 184, 185, 187,
191:1, 208, 210, 245, 247 und 251;191: 1, 208, 210, 245, 247 and 251;
C.I. Pigment Yellow 1, 3, 62, 65, 73,C.I. Pigment Yellow 1, 3, 62, 65, 73,
74, 97, 120, 151, 154, 168, 181, 183 und74, 97, 120, 151, 154, 168, 181, 183 and
191;191;
C.I. Pigment Violet 32;C.I. Pigment violet 32;
- Disazopigmente: C.I. Pigment Orange 16, 34, 44 und 72; C.I. Pigment Red 144, 166, 214, 220, 221 und 242;- Disazo pigments: C.I. Pigment Orange 16, 34, 44 and 72; C.I. Pigment Red 144, 166, 214, 220, 221 and 242;
C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180 und 188;C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180 and 188;
Disazokondensations- pigmente : C.I. Pigment Yellow 93, 95 und 128;Disazo condensation pigments: C.I. Pigment Yellow 93, 95 and 128;
C.I. Pigment Red 144, 166, 214, 220', 242 und 262;CI Pigment Red 144, 166, 214, 220 ' , 242 and 262;
C.I. Pigment Brown 23 und 41; - Anthanthronpigmente: C.I. Pigment Red 168;CI Pigment Brown 23 and 41; - Anthanthrone pigments: CI Pigment Red 168;
- Anthrachinonpigmente : C.I. Pigment Yellow 147, 177 und 199;- Anthraquinone pigments: C.I. Pigment Yellow 147, 177 and 199;
C.I. Pigment Violet 31;C.I. Pigment violet 31;
- Anthrapyrimidin- pigmente : C.I. Pigment Yellow 108;- Anthrapyrimidine pigments: C.I. Pigment yellow 108;
- Chinacridonpigmente: C.I. Pigment Orange 48 und 49; C.I. Pigment Red 122, 202, 206 und 209;- Quinacridone pigments: C.I. Pigment Orange 48 and 49; C.I. Pigment Red 122, 202, 206 and 209;
C.I. Pigment Violet 19;C.I. Pigment violet 19;
- Chinophthalonpigmente: C.I. Pigment Yellow 138;- Quinophthalone pigments: C.I. Pigment yellow 138;
- Diketopyrrolopyrrol- pigmente : C.I. Pigment Orange 71, 73 und 81;- Diketopyrrolopyrrole pigments: C.I. Pigment Orange 71, 73 and 81;
C.I. Pigment Red 254, 255, 264, 270 undC.I. Pigment Red 254, 255, 264, 270 and
272;272;
- Dioxazinpigmente: C.I. Pigment Violet 23 und 37; C.I. Pigment Blue 80;- Dioxazine pigments: C.I. Pigment violet 23 and 37; C.I. Pigment blue 80;
- Flavanthronpigmente: C.I. Pigment Yellow 24;- Flavanthrone pigments: C.I. Pigment yellow 24;
- Indanthronpigmente: C.I. Pigment Blue 60 und 64;- Indanthrone pigments: C.I. Pigment Blue 60 and 64;
- Isoindolinpigmente: C.I. Pigmente Orange 61 und 69;- Isoindoline pigments: C.I. Pigments Orange 61 and 69;
C.I. Pigment Red 260;C.I. Pigment Red 260;
C.I. Pigment Yellow 139 und 185;C.I. Pigment Yellow 139 and 185;
- Isoindolinonpigmente: C.I. Pigment Yellow 109, 110 und 173;- Isoindolinone pigments: C.I. Pigment Yellow 109, 110 and 173;
- Isoviolanthronpigmente: C.I. Pigment Violet 31;- Isoviolanthrone Pigments: C.I. Pigment violet 31;
- Metallkomplexpigmente: C.I. Pigment Red 257;- Metal complex pigments: C.I. Pigment Red 257;
C.I. Pigment Yellow 117, 129, 150, 153 und 177;C.I. Pigment Yellow 117, 129, 150, 153 and 177;
C.I. Pigment Green 8 ;C.I. Pigment green 8;
- Perinonpigmente : C.I. Pigment Orange 43; C.I. Pigment Red 194;- Perinone pigments: C.I. Pigment orange 43; C.I. Pigment Red 194;
- Perylenpigmente: C.I. Pigment Black 31 und 32;- Perylene pigments: C.I. Pigment black 31 and 32;
C.I. Pigment Red 123, 149, 178, 179, 190 und 224;C.I. Pigment Red 123, 149, 178, 179, 190 and 224;
C.I. Pigment Violet 29; Phthalocyaninpigmente : C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 und 16; C.I. Pigment Green 7 und 36;CI Pigment Violet 29; Phthalocyanine Pigments: CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; CI Pigment Green 7 and 36;
Pyranthronpigmente : C.I. Pigment Orange 51; C.I. Pigment Red 216;Pyranthrone Pigments: C.I. Pigment Orange 51; C.I. Pigment red 216;
- Pyrazolochinazolon- pigmente : C.I. Pigment Orange 67;- Pyrazoloquinazolone pigments: C.I. Pigment orange 67;
C.I. Pigment Red 251;C.I. Pigment Red 251;
- Thioindigopigmente: C.I. Pigment Red 88 und 181;- Thioindigo pigments: C.I. Pigment Red 88 and 181;
C.I. Pigment Violet 38;C.I. Pigment violet 38;
- Triarylcarbonium- pigmente : C.I. Pigment Blue 1, 61 und 62;- Triarylcarbonium pigments: C.I. Pigment Blue 1, 61 and 62;
C.I. Pigment Green 1;C.I. Pigment green 1;
C.I. Pigment Red 81, 81:1 und 169;C.I. Pigment Red 81, 81: 1 and 169;
C.I. Pigment Violet 1, 2, 3 und 27;C.I. Pigment violet 1, 2, 3 and 27;
- C.I. Pigment Black 1 (Anilinschwarz);- C.I. Pigment Black 1 (aniline black);
- C.I. Pigment Yellow 101 (Aldazingelb) ;- C.I. Pigment Yellow 101 (Aldazine Yellow);
- C.I. Pigment Brown 22.- C.I. Pigment Brown 22
Geeignete anorganische Farbpigmente sind z.B.Suitable inorganic color pigments are e.g.
- Weißpigmente: Titandioxid (C.I. Pigment White 6), Zinkweiß, Farbenzinkoxid; Zinksulfid, Lithopone;- White pigments: titanium dioxide (C.I. Pigment White 6), zinc white, colored zinc oxide; Zinc sulfide, lithopone;
- Schwarzpigmente : Eisenoxidschwarz (C.I. Pigment Black 11),- black pigments: iron oxide black (C.I. Pigment Black 11),
Eisen-Mangan-Schwarz , Spinellschwarz (C.I. Pigment Black 27); Ruß (C.I. Pigment Black 7) ;Iron-manganese black, spinel black (C.I. Pigment Black 27); Carbon black (C.I. Pigment Black 7);
- Buntpigmente : Chromoxid, Chromoxidhydratgrün; Chromgrün (C.I. Pigment Green 48); Co- baltgrün (C.I. Pigment Green 50); Ultramaringrün;- Colored pigments: chromium oxide, chromium oxide hydrate green; Chrome green (C.I. Pigment Green 48); Cobalt green (C.I. Pigment Green 50); Ultramarine green;
Kobaltblau (C.I.. Pigment Blue 28 und 36; C.I. Pigment Blue 72); Ultramarinblau; Manganblau; Ultramarinviolett; Kobalt- und Manganviolett;Cobalt blue (CI. Pigment Blue 28 and 36; CI Pigment Blue 72); Ultramarine blue; Manganese blue; Ultramarine violet; Cobalt and manganese violet;
Eisenoxidrot (C.I. Pigment Red 101); Cadmiumsulfoselenid (C.I. Pigment RedIron oxide red (C.I. Pigment Red 101); Cadmium sulfoselenide (C.I. Pigment Red
108); Cersulfid (C.I. Pigment Red 265); Molybdatrot (C.I. Pigment Red 104); Ultramarinrot;108); Cerium sulfide (C.I. Pigment Red 265); Molybdate red (C.I. Pigment Red 104); ultramarine;
Eisenoxidbraun (C.I. Pigment Brown 6 undIron oxide brown (C.I. Pigment Brown 6 and
7) , Mischbraun, Spinell- und Korundphasen (C.I. Pigment Brown 29, 31, 33, 34, 35, 37, 39 und 40), Chromtitangelb (C.I. Pigment Brown 24) , Chromorange;7), mixed brown, spinel and corundum phases (C.I. Pigment Brown 29, 31, 33, 34, 35, 37, 39 and 40), chrome titanium yellow (C.I. Pigment Brown 24), chrome orange;
Cersulfid (C.I. Pigment Orange 75); Eisenoxidgelb (C.I. Pigment Yellow 42); Nickeltitangelb (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 und 189); Chromtitangelb; Spinellphasen (C.I. Pigment Yellow 119) ; Cadmiumsulfid und Cadmiumzinksul- fid (C.I. Pigment Yellow 37 und 35); Chromgelb (C.I. Pigment Yellow 34); Bismutvanadat (C.I. Pigment Yellow 184) .Cerium sulfide (C.I. Pigment Orange 75); Iron oxide yellow (C.I. Pigment Yellow 42); Nickel titanium yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); Chromium titanium yellow; Spinel phases (C.I. Pigment Yellow 119); Cadmium sulfide and cadmium zinc sulfide (C.I. Pigment Yellow 37 and 35); Chrome yellow (C.I. Pigment Yellow 34); Bismuth vanadate (C.I. Pigment Yellow 184).
Als Beispiele für üblicherweise als Füllstoffe eingesetzte anorganische Pigmente seien transparentes Siliciumdioxid, Quarzmehl, Aluminiumoxid, Aluminiumhydroxid, natürliche Glimmer, natürliche und gefällte Kreide und Bariumsulfat genannt.Examples of inorganic pigments commonly used as fillers are transparent silicon dioxide, quartz powder, aluminum oxide, aluminum hydroxide, natural mica, natural and precipitated chalk and barium sulfate.
Bei den Glanzpigmenten handelt es sich um einphasig oder mehrphasig aufgebaute plättchenförmige Pigmente, deren Farbenspiel • durch das Zusammenspiel von Interferenz-, Reflexions- und Absorp- tionsphänomenen geprägt ist. Als Beispiele seien Aluminium- plättchen und ein- oder mehrfach, insbesondere mit Metalloxiden beschichtete Aluminium-, Eisenoxid- und Glimmerplättchen genannt.The luster pigments are single-phase or multi-phase platelet-shaped pigments whose play of colors is • characterized by the interplay of interference, reflection and absorption phenomena. Examples include aluminum flakes and aluminum, iron oxide and mica flakes coated one or more times, in particular coated with metal oxides.
Als Komponente (B) enthalten die erfindungsgemäß zu verwendenden festen Pigmentzubereitungen oberflächenaktive Additive auf der Basis von Polyethern, die nichtionisch oder anionisch modifiziert sein können. Es können sowohl verschiedene nichtionische als auch verschiedene anionische Additive sowie auch Mischungen von nichtionischen und anionischen Additiven enthalten sein. Anionische oberflächenaktive Additive sind dabei die sauren Phosphorsäure-, Phosphonsäure-, Schwefelsäure- und/oder Sulfonsäureester der Polyether und/oder deren Salze.The solid pigment preparations to be used according to the invention contain, as component (B), surface-active additives based on polyethers, which can be modified nonionically or anionically. Different nonionic and different anionic additives as well as mixtures of nonionic and anionic additives can be contained. Anionic surface-active additives are the acidic phosphoric acid, phosphonic acid, sulfuric acid and / or sulfonic acid esters of the polyethers and / or their salts.
Bei den nichtionischen oberflächenaktiven Additiven auf Poly- etherbasis handelt es insbesondere um Polyalkylenoxide oder Umsetzungsprodukte von Alkylenoxiden mit Alkoholen, Aminen, alipha- tischen Carbonsäuren oder aliphatischen Carbonsäureamiden. Erfindungsgemäß soll dabei unter dem Begriff Alkylenoxid auch arylsubstiutiertes Alkylenoxid, insbesondere phenylsubstituiertes Ethylenoxid, verstanden werden.The nonionic surface-active additives based on polyether are, in particular, polyalkylene oxides or reaction products of alkylene oxides with alcohols, amines, aliphatic carboxylic acids or aliphatic carboxylic acid amides. According to the invention, the term alkylene oxide should also be understood to mean aryl-substituted alkylene oxide, in particular phenyl-substituted ethylene oxide.
Neben den ungemischten Polyalkylenoxiden, vorzugsweise C-C-Alkylenoxiden und phenylsubstituierten C2-C-Alkylenoxiden, wie Polyethylenoxiden, Polypropylenoxiden und Poly (phenylethylen- oxiden) , sind vor allem Alkylenoxidblockcopolymere, aber auch statistische Copolymere dieser Alkylenoxide als Komponente (B) geeignet .In addition to the unmixed polyalkylene oxides, preferably CC alkylene oxides and phenyl-substituted C 2 -C alkylene oxides, such as polyethylene oxides, polypropylene oxides and poly (phenyl ethylene oxides), alkylene oxide block copolymers, but also random copolymers of these alkylene oxides, are particularly suitable as component (B).
Ganz besonders geeignet sind dabei Blockcopolymere, die Polypropylenoxid- und Polyethylenoxidblöcke oder auch Poly(phenyl- ethylenoxid) - und Polyethylenoxidblöcke aufweisen. Sie können wie die ungemischten Polyalkylenoxide durch Polyaddition der Alkylenoxide an Starterverbindungen, wie gesättigte oder ungesättigte aliphatische und aromatische Alkohole, gesättigte oder ungesättigte aliphatische und aromatische Amine, gesättigte oder ungesättigte aliphatische Carbonsäuren und Carbonsäureamide, erhalten werden. Bei Einsatz von Ethylenoxid und Propylenoxid können diese Starterverbindungen zunächst mit Ethylenoxid und dann mit Propylenoxid oder vorzugsweise zunächst mit Propylenoxid und dann mit Ethylenoxid umgesetzt werden. Üblicherweise werden 1 bis 300 ol, bevorzugt 3 bis 150 ol, Alkylenoxid je mol Startermolekül eingesetzt.Block copolymers which have polypropylene oxide and polyethylene oxide blocks or else poly (phenylethylene oxide) and polyethylene oxide blocks are very particularly suitable. Like the unmixed polyalkylene oxides, they can be obtained by polyaddition of the alkylene oxides to starter compounds, such as saturated or unsaturated aliphatic and aromatic alcohols, saturated or unsaturated aliphatic and aromatic amines, saturated or unsaturated aliphatic carboxylic acids and carboxamides. When using ethylene oxide and propylene oxide, these starter compounds can first be reacted with ethylene oxide and then with propylene oxide or preferably first with propylene oxide and then with ethylene oxide. Usually 1 to 300 ol, preferably 3 to 150 ol, of alkylene oxide are used per mol of starter molecule.
Geeignete aliphatische Alkohole enthalten dabei in der Regel 6 bis 26 C-Atome, bevorzugt 8 bis 18 C-Atome, und können unverzweigt, verzweigt oder cyclisch aufgebaut sein. Als Beispiele seien Octanol, Nonanol, Decanol, Isodecanol, Undecanol, Dodecanol, 2-Butyloctanol, Tridecanol, Isotridecanol, Tetra- decanol, Pentadecanol, Hexadecanol, 2-Hexyl ecanol, Heptadecanol , Octadecanol, 2-Heptylundecanol, 2-Octyldecanol, 2-Nonyltridecanol, 2-Decyltetradecanol, Oleylalkohol und 9-Octadecenol sowie auch Mischungen dieser Alkohole wie Cg/Cio-/ C13/C15- und Ciβ/Ciβ-Alkohole, und Cyclopentanol und Cyclohexanol genannt. Von besonderem Interesse sind die gesättigten und ungesättigten Fettalkohole, die durch Fettspaltung und Reduktion aus natürlichen Rohstoffen gewonnen werden, und die synthetischen Fettalkohole aus der Oxosynthese. Die Alkylenoxidaddukte an diese Alkohole weisen üblicherweise mittlere Molekulargewichte Mn von 200 bis 5000, vor allem von 400 bis 2000, auf.Suitable aliphatic alcohols generally contain 6 to 26 carbon atoms, preferably 8 to 18 carbon atoms, and can be unbranched, branched or cyclic. Examples include octanol, nonanol, decanol, isodecanol, undecanol, dodecanol, 2-butyloctanol, tridecanol, isotridecanol, tetra-decanol, pentadecanol, hexadecanol, 2-hexyl ecanol, heptadecanol, octadecanol, 2-heptylundecanol, 2-octyldecanol and 2-octyldecanol. Nonyltridecanol, 2-decyltetradecanol, oleyl alcohol and 9-octadecenol and also mixtures of these alcohols such as Cg / Cio- / C 13 / C 15 - and Ciβ / Ciβ-alcohols, and cyclopentanol and cyclohexanol. Of particular interest are the saturated and unsaturated fatty alcohols, which are obtained from natural raw materials through fat splitting and reduction, and the synthetic fatty alcohols from oxosynthesis. The alkylene oxide adducts with these alcohols usually have average molecular weights M n of 200 to 5000, especially 400 to 2000.
5 Als Beispiele für die obengenannten aromatischen Alkohole seien neben - und ß-Naphthol und deren Cι-C-Alkylderivaten insbesondere Phenol und seine Cχ-Ci2-Alkylderivate, wie Hexylphenol, Heptylphenol , Octylphenol, Nonylphenol, Isononylphenol, Undecyl- phenol, Dodecylphenol, Di- und Tributylphenol und Dinonylphenol 10 genannt .5 Examples of the above-mentioned aromatic alcohols include, in addition to - and ß-naphthol and their C 1 -C 4 -alkyl derivatives, especially phenol and its Cχ-Ci 2 alkyl derivatives, such as hexylphenol, heptylphenol, octylphenol, nonylphenol, isononylphenol, undecylphenol, dodecylphenol, Di- and tributylphenol and dinonylphenol 10 called.
Geeignete aliphatische Amine entsprechen den oben aufgeführten aliphatiεchen Alkoholen. Besondere Bedeutung haben auch hier die gesättigten und ungesättigten Fettamine, die vorzugsweise 14 bis 15 20 C-Atome aufweisen. Als aromatische Amine seien beispielsweise Anilin und Benzidin und deren Derivate genannt.Suitable aliphatic amines correspond to the aliphatic alcohols listed above. Here too, the saturated and unsaturated fatty amines, which preferably have 14 to 15 20 C atoms, are of particular importance. Aniline and benzidine and their derivatives may be mentioned as aromatic amines.
Als aliphatische Carbonsäuren eignen sich insbesondere gesättigte und ungesättigte Fettsäuren, die bevorzugt 14 bis 20 C-Atome ent- 20 halten, und hydrierte, teilhydrierte und unhydrierte Harzsäuren sowie auch mehrwertige Carbonsäuren, z.B. Dicarbonsäuren, wie Maleinsäure .Suitable aliphatic carboxylic acids are, in particular, saturated and unsaturated fatty acids, which preferably contain 14 to 20 C atoms, and hydrogenated, partially hydrogenated and unhydrogenated resin acids and also polyvalent carboxylic acids, e.g. Dicarboxylic acids such as maleic acid.
Geeignete Carbonsäureamide leiten sich von diesen Carbonεäuren 25 ab.Suitable carboxamides are derived from these carboxylic acids 25.
Neben den Alkylenoxidaddukten an diese einwertigen Amine und Alkohole sind die Alkylenoxidaddukte an mindestens bifunktioneile Amine und Alkohole von ganz besonderem Interesse.In addition to the alkylene oxide adducts with these monohydric amines and alcohols, the alkylene oxide adducts with at least bifunctional amines and alcohols are of particular interest.
3030
Als mindestens bifunktionelle Amine sind zwei- bis fünfwertige Amine bevorzugt, die insbesondere der Formel H2N- (R-NR1) n-H (R: C2-C6-Alkylen; R1 : Wasserstoff oder Ci-Cδ-Alkyl ; n: 1 bis 5) entsprechen. Im einzelnen seien beispielhaft genannt: Ethylendiamin,Preferred at least bifunctional amines are di- to pentavalent amines, which in particular have the formula H 2 N- (R-NR 1 ) n -H (R: C 2 -C 6 alkylene; R 1 : hydrogen or Ci-C δ - Alkyl; n: 1 to 5) correspond. Examples include: ethylenediamine,
35 Diethylentriamin, Triethylentetramin, Tetraethylenpentamin,35 diethylene triamine, triethylene tetramine, tetraethylene pentamine,
Propylendiamin-1, 3 , Dipropylentriamin, 3-Amino-l-ethylenaminopro- pan, Hexamethylendiamin, Dihexamethylentriamin, 1, 6-Bis- (3-amino- propylamino)hexan und N-Methyldipropylentriamin, wobei Hexamethylendiamin und Diethylentriamin besonders bevorzugt sind undPropylenediamine-1,3, dipropylenetriamine, 3-amino-l-ethyleneaminopropane, hexamethylenediamine, dihexamethylenetriamine, 1,6-bis (3-aminopropylamino) hexane and N-methyldipropylenetriamine, with hexamethylenediamine and diethylenetriamine being particularly preferred and
40 Ethylendiamin ganz besonders bevorzugt ist.40 ethylenediamine is very particularly preferred.
Vorzugsweise werden diese Amine zunächst mit Propylenoxid und anschließend mit Ethylenoxid umgesetzt. Der Gehalt der Block- copolymere an Ethylenoxid liegt üblicherweise bei etwa 10 bis 90 5 Gew.-%. Die Blockcopolymere auf Basis mehrwertiger Amine weisen in der Regel mittlere Molekulargewichte Mn von 1000 bis 40000, vorzugsweise 1500 bis 30000, auf.These amines are preferably first reacted with propylene oxide and then with ethylene oxide. The ethylene oxide content of the block copolymers is usually about 10 to 90 5% by weight. The block copolymers based on polyvalent amines generally have average molecular weights M n of 1,000 to 40,000, preferably 1,500 to 30,000.
Als mindestens bifunktionelle Alkohole sind zwei- bis fünfwertige Alkohole bevorzugt. Beispielsweise seien C2-C6-Alkylenglykole und die entsprechenden Di- und Polyalkylenglykole, wie Ethylenglykol, Propylenglykol-1, 2 und -1,3, Butylenglykol-1, 2 und -1,4, Hexylen- glykol-1,6, Dipropylenglykol und Polyethylenglykol , Glycerin und Pentaerythrit sowie Bisphenol-A genannt, wobei Ethylenglykol und Polyethylenglykol besonders bevorzugt und Propylenglykol und Dipropylenglykol ganz besonders bevorzugt sind.Dihydric to pentavalent alcohols are preferred as at least bifunctional alcohols. Examples include C 2 -C 6 alkylene glycols and the corresponding di- and polyalkylene glycols, such as ethylene glycol, propylene glycol-1, 2 and -1.3, butylene glycol-1, 2 and -1.4, hexylene glycol-1,6, Dipropylene glycol and polyethylene glycol, glycerol and pentaerythritol and bisphenol-A are mentioned, ethylene glycol and polyethylene glycol being particularly preferred and propylene glycol and dipropylene glycol being very particularly preferred.
Besonders bevorzugte Alkylenoxidaddukte an mindestens bifunktio- nelle Alkohole weisen einen zentralen Polypropylenoxidblock auf, gehen also von einem Propylenglykol oder Polypropylenglykol aus, das zunächst mit weiterem Propylenoxid und dann mit Ethylenoxid umgesetzt wird. Der Gehalt der Blockcopolymere an Ethylenoxid liegt üblicherweise bei 10 bis 90 Gew.-%.Particularly preferred alkylene oxide adducts with at least bifunctional alcohols have a central polypropylene oxide block, that is to say they start from a propylene glycol or polypropylene glycol which is first reacted with further propylene oxide and then with ethylene oxide. The ethylene oxide content of the block copolymers is usually from 10 to 90% by weight.
Die Blockcopolymere auf Basis mehrwertiger Alkohole weisen im allgemeinen mittlere Molekulargewichte Mn von 1000 bis 20000, vorzugsweise 1000 bis 15000, auf.The block copolymers based on polyhydric alcohols generally have average molecular weights M n of 1000 to 20,000, preferably 1000 to 15,000.
Derartige Alkylenoxidblockcopolymere sind bekannt und im Handel z.B. unter den Namen Tetronic und Pluronic (BASF) erhältlich.Such alkylene oxide block copolymers are known and commercially available e.g. available under the names Tetronic and Pluronic (BASF).
Bei den anionischen oberflächenaktiven Additiven (B) handelt es ' sich um die Sulfonate, Sulfate, Phosphonate und Phosphate der Polyether.The anionic surface-active additives (B) are the sulfonates, sulfates, phosphonates and phosphates of the polyethers.
Die Polyether können durch Umsetzung mit Phosphorsäure, Phosphor- pentoxid und Phosphonsäure bzw. Schwefelsäure und Sulfonsäure in die Phosphorsäuremono- oder -diester und Phosphonsäureester bzw. die Schwefelsäuremonoester und Sulfonsäureester überführt werden. Diese sauren Ester liegen bevorzugt in Form wasserlöslicher Salze, insbesondere als Alkalimetallsalze, vor allem Natriumsalze, und Ammoniumsalze vor, sie können jedoch auch in Form der freien Säuren eingesetzt werden.The polyethers can be converted into the phosphoric acid monoesters or diesters and phosphonic acid esters or the sulfuric acid monoesters and sulfonic acid esters by reaction with phosphoric acid, phosphorus pentoxide and phosphonic acid or sulfuric acid and sulfonic acid. These acidic esters are preferably in the form of water-soluble salts, especially as alkali metal salts, especially sodium salts, and ammonium salts, but they can also be used in the form of the free acids.
Bevorzugte Phosphate und Phosphonate leiten sich vor allem von alkoxylierten, insbesondere ethoxylierten, Fett- und Oxo- alkoholen, Alkylphenolen, Fettaminen, Fettsäuren und Harzsäu en ab, bevorzugte Sulfate und Sulfonate basieren insbesondere auf alkoxylierten, vor allem ethoxylierten, Fettalkoholen, Alkyl- phenolen und A inen, auch mehrwertigen A inen, wie Hexamethylen- diamin.Preferred phosphates and phosphonates are derived primarily from alkoxylated, in particular ethoxylated, fatty and oxo alcohols, alkylphenols, fatty amines, fatty acids and resin acids, preferred sulfates and sulfonates are based in particular on alkoxylated, especially ethoxylated, fatty alcohols, alkyl alcohols. phenols and amines, including polyvalent amines, such as hexamethylene diamine.
Derartige anionische oberflächenaktive Additive sind bekannt und im Handel z.B. unter den Namen Nekal® (BASF), Tamol® (BASF), Cro- dafos® (Croda) , Rhodafac® (Rhodia) , Maphoε® (BASF) , Texapon® (Co- gnis), Empicol® (Albright & Wilson) , Matexil® (ICI) , Soprophor® (Rhodia) und Lutensit® (BASF) erhältlich.Such anionic surface active additives are known and commercially available for example under the name Nekal ® (BASF), Tamol ® (BASF), Cro dafos ® (Croda), Rhodafac ® (Rhodia), Maphoε ® (BASF), Texapon ® (co gnis), Empicol ® (Albright & Wilson), Matexil ® (ICI), Soprophor ® (Rhodia) and Lutensit ® (BASF).
Die erfindungsgemäß zu verwendenden Pigmentzubereitungen enthalten 60 bis 90 Gew.-%, bevorzugt 70 bis 85 Gew.-%, der KomponenteThe pigment preparations to be used according to the invention contain 60 to 90% by weight, preferably 70 to 85% by weight, of the component
(A) und 10 bis 40 Gew.-%, vorzugsweise 15 bis 30 Gew.-%, der Komponente (B) .(A) and 10 to 40% by weight, preferably 15 to 30% by weight, of component (B).
Die erfindungsgemäß zu verwendenden Pigmentzubereitungen können vorteilhaft hergestellt werden, indem man das Pigment (A) zunächst in wäßriger, zumindest einen Teil des oder der AdditiveThe pigment preparations to be used in accordance with the invention can advantageously be prepared by initially pigmenting (A) in aqueous, at least part of, the additive (s)
(B) enthaltender Suspension einer Naßzerkleinerung unterwirft und die Suspension dann, gegebenenfalls nach Zugabe der restlichen Menge Additiv (B) , trocknet.(B) containing suspension is subjected to wet comminution and the suspension is then dried, optionally after addition of the remaining amount of additive (B).
Das Pigment (A) kann dabei als trockenes Pulver oder in Form eines Preßkuchens eingesetzt werden.The pigment (A) can be used as a dry powder or in the form of a press cake.
Bei dem eingesetzten Pigment (A) handelt es sich vorzugsweise um ein gefinishtes Produkt, d.h. die Primärkorngröße des Pigments ist bereits auf den für die Anwendung gewünschten Wert eingestellt. Dieser Pigmentfinish empfiehlt sich insbesondere bei organischen Pigmenten, da die bei der Pigmentsynthese anfallende Rohware in der Regel nicht direkt für die Anwendung geeignet ist. Bei anorganischen Pigmenten, z.B. bei Oxid- und Bismutvanadatpig- menten, kann die Einstellung der Primärkorngröße auch bei der Pigmentsynthese erfolgen, so daß die anfallenden Pigmentsuspensionen direkt zur Herstellung der erfindungsgemäß zu ver- wendenden Pigmentzubereitungen eingesetzt werden können.The pigment (A) used is preferably a finished product, i.e. the primary grain size of the pigment is already set to the value desired for the application. This pigment finish is particularly recommended for organic pigments, since the raw material obtained during pigment synthesis is generally not suitable for the application. In the case of inorganic pigments, e.g. in the case of oxide and bismuth vanadate pigments, the primary grain size can also be set during pigment synthesis, so that the pigment suspensions obtained can be used directly for the preparation of the pigment preparations to be used according to the invention.
Da das gefinishte Pigment (A) bei der Trocknung bzw. auf dem Filteraggregat üblicherweise wieder reagglomeriert, wird es zur Einstellung der eingangs genannten mittleren Teilchengrößen in wäßriger Suspension einer kontinuierlichen oder diskontinuierlichen Naßzerkleinerung, z.B. einer Rührer-, Dissolver- oder Hochdruckhomogenisierung oder Mahlung, insbesondere in einer Rührwerkskugelmühle, unterzogen. Bei der Naßzerkleinerung sollte zumindest ein Teil des oder der in der fertigen Pigmentzubereitung enthaltenen Additive (B) anwesend sein, vorzugsweise setzt man die gesamte Menge Additiv (B) vor der Naßzerkleinerung zu.Since the finished pigment (A) usually reaglomerates again during drying or on the filter unit, it is used to adjust the above-mentioned average particle sizes in aqueous suspension of continuous or discontinuous wet comminution, for example a stirrer, dissolver or high-pressure homogenization or grinding, in particular in an agitator ball mill. At least one part of the additive (B) contained in the finished pigment preparation should be present during the wet comminution, preferably the entire amount of additive (B) is added before the wet comminution.
In Abhängigkeit von der zur Trocknung der wäßrigen Pigment- suspenεion gewählten Methode - Sprühgranulierung und Wirbelschichttrocknung, Sprühtrocknung, Trocknung im Schaufeltrockner, Eindampfen und anschließende Zerkleinerung - kann die Teilchen- große der erfindungsgemäßen PigmentZubereitungen gezielt gesteuert werden.Depending on the method chosen for drying the aqueous pigment suspension - spray granulation and fluidized-bed drying, spray drying, drying in a paddle dryer, evaporation and subsequent comminution - the particle size of the pigment preparations according to the invention can be controlled in a targeted manner.
Bei Sprüh- und Wirbelεchichtgranulierung können grobteilige Granulate mit mittleren Korngrößen von 50 biε 5000 m, inεbeεondere 100 biε 1000 um, erhalten werden. Durch Sprühtrocknung werden üblicherweise Granulate mit mittleren Korngrößen < 20 μm erhalten. Feinteilige Zubereitungen können bei der Trocknung im Schaufeltrockner und beim Eindampfen mit anschließender Mahlung erhalten werden. Vorzugsweise liegen die erfindungsgemäß verwendeten Pigmentzubereitungen jedoch in Granulatform vor, wobei die grob- teiligen Granulate besonders bevorzugt sind.In the case of spray and fluidized bed granulation, coarse-particle granules with average grain sizes of 50 to 5000 m, in particular 100 to 1000 μm, can be obtained. Spray drying usually gives granules with average grain sizes <20 μm. Finely divided preparations can be obtained by drying in a paddle dryer and by evaporation with subsequent grinding. However, the pigment preparations used according to the invention are preferably in granule form, the coarse-particle granules being particularly preferred.
Di Sprühgranulierung führt man vorzugsweise in einem Sprühturm mit Eins offdüse durch. Die Suspenεion wird hier in Form größerer Tropfen verεprüht, wobei das Wasεer verdampft. Daε bzw. die Additive (B) schmelzen bei den Trocknungstemperaturen auf und führen so zur Bildung eines weitgehend kugelförmigen Granulats mit besonders glatter Oberfläche (BET-Werte von in der Regel < 15 m2/g, insbesondere < 10 m2/g) , das erfindungsgemäß bevorzugt ist.The spray granulation is preferably carried out in a spray tower with a one-off nozzle. The suspension is sprayed here in the form of larger drops, the water evaporating. Daε or the additives (B) melt at the drying temperatures and thus lead to the formation of largely spherical granules with a particularly smooth surface (BET values of generally <15 m 2 / g, in particular <10 m 2 / g), which is preferred according to the invention.
Die Gaεeintrittstemperatur im Sprühturm liegt im allgemeinen bei 180 biε 300°C, bevorzugt bei 150 bis 300°C. Die Gasaustrittε- temperatur beträgt in der Regel 70 bis 150°C, vorzugsweise 70 bis 130°C.The gas inlet temperature in the spray tower is generally from 180 to 300 ° C., preferably from 150 to 300 ° C. The gas outlet temperature is generally 70 to 150 ° C., preferably 70 to 130 ° C.
Die Restfeuchte deε erhaltenen Pigmentgranulatε liegt in der Regel bei < 2 Gew.-%.The residual moisture of the pigment granules obtained is generally <2% by weight.
Die Pigmentzubereitungen können vorteilhaft zur Einfärbung von Kunεtεtoffen aller Art verwendet werden. Beispielhaft seien folgende Kunstεtoffklassen und Kunststofftypen genannt: abgewandelte Naturεtoffe:The pigment preparations can advantageously be used for coloring all kinds of plastics. The following plastic classes and types are mentioned as examples: modified natural substances:
Duroplaεte, z.B. Caεein-Kunstεtoffe; Thermoplaste, z.B. Cel- luloεenitrat, Celluloεeacetat, Cellulosemischester und Celluloseether;Duroplaεte, e.g. Caεein-Kunstεtoffe; Thermoplastics, e.g. Cellulose nitrate, cellulose acetate, mixed cellulose esters and cellulose ether;
εynthetiεche Kunststoffe:Synthetic plastics:
Polykondensate : Duroplaεte, z.B. Phenolharz , Harnstoffharz , Thioharnstoffharz, Melaminharz, ungesättigtes Polyesterharz, Allylharz, Silicon, Polyi'mid und Polybenzimidazol; Thermoplaste, z.B. Polyamid, Polycarbonat, Polyester, Polyphenylen- oxid, Polysulfon und Polyvinylacetal;Polycondensates: Duroplaεte, for example, phenol resin, urea resin, thiourea, melamine resin, unsaturated polyester resin, allyl resin, silicone, Poly I 'mid and polybenzimidazole; Thermoplastics, for example polyamide, polycarbonate, polyester, polyphenylene oxide, polysulfone and polyvinyl acetal;
Polymerisate: Thermoplaste, z.B. Polyolefine, wie Poly- ethylen, Polypropylen, Poly-1-buten und Poly-4-methyl- 1-penten, Ionomere, Polyvinylchlorid, Polyvinylidenchlorid, Polymethylmethacrylat, Polyacrylnitril, Polystyrol, Poly- acetal', Fluorkunstεtoffe, Polyvinylalkohol , Polyvinylacetat und Poly-p-xylylen εowie Copolymere, wie Ethylen/Vinylacetat- Copolymere, Styrol/Acrylnitril-Copolymere, Acrylnitril/Butadien/Styrol-Copolymere, Polyethylenglykolterephthalat und Po- lybutylenglykolterephthalat;Polymers: thermoplastics, e.g. Polyolefins, such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene, ionomers, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, polyacrylonitrile, polystyrene, polyacetal ', fluoroplastics, polyvinyl alcohol, polyvinyl acetate and polyvinyl p-xylylene and copolymers, such as ethylene / vinyl acetate copolymers, styrene / acrylonitrile copolymers, acrylonitrile / butadiene / styrene copolymers, polyethylene glycol terephthalate and polybutylene glycol terephthalate;
Polyaddukte: Duroplaεte, z.B. Epoxidharz und vernetzte Polyurethane; Thermoplaste, z.B. lineare Polyurethane und chlorierte Polyether.Polyadducts: Duroplaεte, e.g. Epoxy resin and cross-linked polyurethane; Thermoplastics, e.g. linear polyurethanes and chlorinated polyethers.
Die erfindungsgemäß zu verwendenden festen Pigmentzubereitungen zeichnen sich bei der Einarbeitung in Kunststoffe durch ihre besonders leichte Diεpergierbarkeit auε . Dieε gilt inεbesondere auch für die erfindungsgemäß bevorzugt zu verwendenden Pigmentzubereitungen in Granulatform, welche sich durch folgende zusätzliche vorteilhafte Eigenschaften auεzeichnen: auεgezeichnete Abriebfeεtigkeit, geringe Kompaktierungε- bzw. Verklumpungεnei- gung, gleichmäßige Kornverteilung, gute Schutt-, Riesel- und Do- εierfähigkeit sowie Staubfreiheit bei Handling und Applikation. Die Kunststoffe können vorteilhaft unter geringem Energieeintrag, z.B. durch gemeinsames Extrudieren (vorzugsweise mit einem Ein- oder ZweiSchneckenextruder) , Walzen, Kneten oder Mahlen, mit den Pigmentzubereitungen eingefärbt werden. Sie können dabei alε pla- εtische Masεen oder Schmelzen vorliegen und zu Kunεtstofformkör- pern, Folien und Fasern verarbeitet werden.When incorporated into plastics, the solid pigment preparations to be used according to the invention are notable for their particularly easy dispersibility. This also applies in particular to the pigment preparations in granular form which are preferably to be used according to the invention and which are distinguished by the following additional advantageous properties: excellent abrasion resistance, low tendency to compact or clump, uniform particle size distribution, good debris, free-flowing and metering capacity and freedom from dust in handling and application. The plastics can advantageously with little energy input, e.g. by extruding them together (preferably using a single or twin screw extruder), rolling, kneading or grinding, with the pigment preparations. They can exist as plastic masses or melts and can be processed into plastic moldings, foils and fibers.
Zudem zeichnen sich die erfindungsgemäß zu verwendenden feεten Pigmentzubereitungen durch inεgesamt vorteilhafte Anwendungseigenschaften, vor allem gute koloristiεche Eigenεchaften, ins- beεondere hohe Farbstärke und Brillanz, und die guten rheolo- giεchen Eigenschaften der mit ihnen eingefärbten Kunststoffe, inεbeεondere niedrige Druckfilterwerte (hohe Filterεtandszeiten) und gute Verspinnbarkeit, aus.In addition, the solid pigment preparations to be used according to the invention are distinguished by generally advantageous application properties, especially good color properties, in particular particularly high color strength and brilliance, and the good rheological properties of the plastics colored with them, in particular low pressure filter values (high filter service life) and good spinnability.
Selbstverständlich können sie sowohl zur Direkteinfärbung von Kunststoffen als auch zur Einfärbung von Masterbatches und Compounds verwendet werden. Bei der Kunststoffdirekteinfärbung kommen sie in der Regel in Mengen von 0,1 bis 5 Gew.-%, bezogen auf den einzufärbenden Kunststoff, zum Einsatz, bei der Einfärbung von Masterbatches können bis zu 70 Gew.-% Pigmentzubereitung, bezogen auf den einzufärbenden Kunstεtoff, eingesetzt werden.Of course, they can be used for direct coloring of plastics as well as for coloring masterbatches and compounds. In direct plastic coloring, they are generally used in quantities of 0.1 to 5% by weight, based on the plastic to be colored. When coloring masterbatches, up to 70% by weight pigment preparation, based on the plastic to be colored, can be used , are used.
BeispieleExamples
Herstellung von Pigmentzubereitungen in Granulatform und deren Anwendung zur Einfärbung von KunststoffenManufacture of pigment preparations in granular form and their use for coloring plastics
Die Herstellung der Pigmentgranulate erfolgte, indem eineThe pigment granules were produced by a
Suspension von 80 kg gefinishtem Pigment (A) und x kg Additiv (B) in 150 kg Wasser in einer Kugelmühle auf einen dso-Wert von < 1 μ gemahlen und dann in einem Sprühturm mit Einstoffdüse (Gas- eintrittεtemperatur 170°C, Gaεauεtrittstemperatur 80°C) sprüh- granuliert wurde. Im Fall des Additivs (B4) wurde die Suspension vor der' Mahlung durch Zugabe von 25 gew.-%iger Natronlauge auf einen pH-Wert von 7 eingestellt.Suspension of 80 kg of finished pigment (A) and x kg of additive (B) in 150 kg of water was ground in a ball mill to a dso value of <1 μ and then in a spray tower with a single-component nozzle (gas inlet temperature 170 ° C., gas outlet temperature 80 ° C) was spray granulated. In the case of the additive (B4), the suspension was% sodium hydroxide solution wt set before the 'grinding by the addition of 25 .- a pH = 7.
Alε Additive wurden dabei eingesetzt:The following additives were used:
Bl : Blockcopolymer auf Basis Ethylendiamin/Propylenoxid/Ethylen- oxid mit einem Ethylenoxidgehalt von 40 Gew.-% und einem mittleren Molekulargewicht Mn von 12000.B1: block copolymer based on ethylenediamine / propylene oxide / ethylene oxide with an ethylene oxide content of 40% by weight and an average molecular weight M n of 12,000.
B2 : Blockcopolymer auf Basis Ethylenoxid/Propylenoxid/Ethylenoxid mit einem Ethylenoxidgehalt von 50 Gew.-% und einem mittleren Molekulargewicht Mn von 6500.B2: block copolymer based on ethylene oxide / propylene oxide / ethylene oxide with an ethylene oxide content of 50% by weight and an average molecular weight M n of 6500.
B3: Blockcopolymer auf Basis Ethylenoxid/Propylenoxid/Ethylenoxid mit einem Ethylenoxidgehalt von 10 Gew.-% und einem mittleren Molekulargewicht Mn von 3500.B3: block copolymer based on ethylene oxide / propylene oxide / ethylene oxide with an ethylene oxide content of 10% by weight and an average molecular weight M n of 3500.
B4 : Saurer Phosphorsäureester auf Basis von alkoxyliertem Cι3-Cι5-Oxoalkohol (6 mol PO und 12 mol EO/mol Alkohol) Zur Beurteilung ihrer Anwendungseigenschaften wurden die erhaltenen Pigmentgranulate in Polyethylen (LDPE) , Weich-PVC und Polypropylen eingearbeitet. Alε Vergleich dienten Auεfärbungen, die mit dem jeweils nicht mit Additiven belegten Pigment erhalten 5 wurden.B4: Acidic phosphoric acid ester based on alkoxylated C 3 -C 5 oxoxalcohol (6 mol PO and 12 mol EO / mol alcohol) The pigment granules obtained were incorporated into polyethylene (LDPE), soft PVC and polypropylene to assess their application properties. As a comparison, stains were obtained which were obtained 5 with the pigment not coated with additives.
Die Bestimmung der koloriεtischen Eigenεchaften erfolgte in Weißaufhellung in LDPE sowie Weich-PVC. Dazu wurden 5 gew.-%ig mit Titandioxid eingefärbtes LDPE bzw. PVC und die jeweilige Pigment- The color properties were determined in white lightening in LDPE and soft PVC. For this purpose, 5% by weight LDPE or PVC colored with titanium dioxide and the respective pigment
10 Zubereitung in dem Aufhellverhältniε 1:10 (0,5 Gew.-% reines Pigment + 5 Gew.-% Titandioxid) vermiεcht und auf einem Miεchwalz- werk bei einer Walzentemperatur von 160°C und 200 Walzenumdrehungen zu einem Walzenfell der Stärke 0,4 mm verarbeitet. Nach Halbierung deε Walzenfells wurde die eine Hälfte weitere 200 Walzen-10 preparation in the brightening ratio 1:10 (0.5% by weight of pure pigment + 5% by weight of titanium dioxide) mixed and on a machine mill at a roller temperature of 160 ° C. and 200 roller revolutions to form a roller skin of thickness 0, 4 mm processed. After halving the roller skin, half of the other 200 roller
15 Umdrehungen bei einer Walzentemperatur von 130°C gewalzt. Die Fellεtärke betrug dabei 0,3 mm. Beide Walzfelle wurden jeweilε zerteilt und in einer Preεse mit Diεtanzrahmen (1 mm) bei 180°C zu Platten gepreßt. Anschließend wurden die Platten unter - Verwendung der Normlichtart D65 farbmetrisch nach der CIELAB-Formel (DINRolled 15 revolutions at a roll temperature of 130 ° C. The fur thickness was 0.3 mm. Each of the rolled skins was cut and pressed into sheets in a press with a distance frame (1 mm) at 180 ° C. The plates were then colorimetrically measured using the standard illuminant D65 according to the CIELAB formula (DIN
20 6174) ausgewertet.20 6174) were evaluated.
Die koloristischen Parameter Farbwinkel H und Chroma C* sowie die Farbstärke (Angabe der Färbeäquivalente FAE) wurden an dem bei 130°C ausdispergierten LDPE- bzw. PVC-Fell bestimmt. Der Auεfär- 25 bung mit dem jeweiligen unbehandelten Pigment wurde der FAE-Wert 100 (Standard) zugeordnet. FAE-Werte < 100 bedeuten eine höhere Farbstärke alε beim Standard, FAE-Werte > 100 entεprechend eine kleinere Farbεtärke. The coloristic parameters color angle H and chroma C * and the color strength (details of the color equivalents FAE) were determined on the LDPE or PVC fur dispersed at 130 ° C. The coloration with the respective untreated pigment was assigned the FAE value 100 (standard). FAE values <100 mean a higher color strength than the standard, FAE values> 100 correspondingly a lower color strength.
30 Zur Prüfung der Diεpergierbarkeit der erhaltenen Pigmentgranulate wurden 2 gew.-%ig pigmentierte LDPE-Blasfolien hergestellt und visuell auf Pigmentstippen untersucht. Die Bewertung in Form der Foliennote (FN) erfolgte anhand einer Skala von 1 (sehr gut) bis 5 (sehr schlecht) .30 To test the dispersibility of the pigment granules obtained, 2% by weight pigmented LDPE blown films were produced and visually examined for pigment specks. The rating in the form of the film grade (FN) was carried out on a scale from 1 (very good) to 5 (very bad).
3535
Die Beεtimmung der Dispergierhärte erfolgte in Weißaufhellung in Weich-PVC. Die dabei untersuchten PVC-Platten wurden wie oben beschrieben hergestellt und farbmetrisch vermessen. Die Berechnung der Dispergierhärte (DH) wurde aus den bei der Messung erhaltenenThe dispersion hardness was determined in white lightening in soft PVC. The PVC sheets investigated were produced as described above and measured colorimetrically. The calculation of the dispersion hardness (DH) was made from those obtained during the measurement
40 Aufhellverhältnissen nach der folgenden Formel vorgenommen:40 lightening ratios according to the following formula:
AVIAVI
DH = - 1 xlOO •AV2DH = - 1 x 100 • AV2
45 AVI: Aufhellverhältnis der bei 130°C hergestellten Färbung AV2 : Aufhellverhältnis der bei 160°C hergestellten Färbung Zur Beεtimmung deε Druckfilterwerteε wurde daε jeweilige Pigmentgranulat zunächst in PE-Wachs dispergiert (40 gew.-%ige Pigmentierung) . Diese Präparation wurde dann mit Polypropylen vorgemischt (2,5 gew.-%ige Pigmentierung), in einem Extruder aufge- schmolzen und mittels einer Spinnpumpe über ein definiertes Filterpaket gefördert .45 AVI: lightening ratio of the color produced at 130 ° C AV2: lightening ratio of the color produced at 160 ° C To determine the pressure filter values, the respective pigment granules were first dispersed in PE wax (40% by weight pigmentation). This preparation was then premixed with polypropylene (2.5% by weight pigmentation), melted in an extruder and conveyed through a defined filter package using a spinning pump.
Der Filtertest wurde wie folgt durchgeführt: Nach dem Einbau der Filterkasεette mit dem Filterpaket wurde bis zur Einstellung des thermiεchen Gleichgewichtε gewartet'. Das Filterpaket wurde dabei so eingesetzt, daß das feine Sieb (Anzahl Kettfäden in 3 , 5 mm: 42; Anzahl Schußfäden in 3 , 5 mm: 17; Maschenzahl: 10870/cm2; absolute Filterfeinheit: 33-37 μm) vom Materialεtrom zuerεt errreicht wurde. Die Anlage wurde dann unter Einsatz von unpig entiertem Polypropylen in Betrieb genommen, wobei der sich vor dem Filter entwickelnde' Druck (Anfangsdruck Pl) ermittelt wurde. Anεchlie- ßend wurde ebenfalls unter Messung des Drucks die Teεt iεchung durch daε Filterpaket gefördert. Durch eventuell vorhandene Feεt- teilchen kann dabei der Druck vor dem Filter ansteigen. Der. höch- ste in dieser Phase erreichte Druck iεt der Enddruck P2. Vor jeder Folgemessung wurde der Extruder durch Nachfahren von unpigmentiertem Polypropylen gereinigt und das Filterpaket ersetzt. Die Berechnung des Druckfilterwerteε (DFW) auε den Druckwerten erfolgte nach folgender Formel (DFW-Werte < 2,0 bar/g gelten -als gut) :The filter test was carried out as follows: after installing the filter cassette with the filter pack, there was a wait until the thermal equilibrium was reached. The filter package was used so that the fine sieve (number of warp threads in 3.5 mm: 42; number of weft threads in 3.5 mm: 17; number of stitches: 10870 / cm 2 ; absolute filter fineness: 33-37 μm) of the material flow was reached. The system was then started up using unpig entiertem polypropylene, the developing before the filter 'pressure (initial pressure Pl) was determined. Subsequently, the measurement was also conveyed through the filter package while measuring the pressure. The pressure upstream of the filter may increase due to any particles present. The. The highest pressure reached in this phase is the final pressure P2. Before each subsequent measurement, the extruder was cleaned with unpigmented polypropylene and the filter package was replaced. The pressure filter values (DFW) were calculated from the pressure values using the following formula (DFW values <2.0 bar / g are considered good):
DFW = P2 Pl [bar/g Pigment]DFW = P2 Pl [bar / g pigment]
Pl : Anfangsdruck [bar] , P2 : Enddruck [bar] G: Pigmentmenge [g]Pl: initial pressure [bar], P2: final pressure [bar] G: amount of pigment [g]
In der folgenden Tabelle sind die Zusammenεetzung der hergeεtell- ten Pigmentgranulate sowie die in den genannten Kunstεtoffen erhaltenen Prüfergebnisse zuεammengeεtellt. Als Vergleich dienen die jeweiligen nicht mit dem Additiv belegten Pigmente, die für ' die Angabe der koloristiεchen Parameter als Standard dienten. H rHThe following table shows the composition of the pigment granules produced and the test results obtained in the plastics mentioned. The respective pigments not coated with the additive serve as a comparison and served as the standard for the specification of the coloristic parameters. H rH
Figure imgf000017_0001
Figure imgf000017_0001

Claims

Patentansprüche claims
1. Verwendung von feεten Pigmentzubereitungen, die als wesentli- ehe Bestandteile1. Use of solid pigment preparations which are essential components
(A) 60 biε 90 Gew.-% mindeεtenε eineε Pig entε und(A) 60 to 90% by weight of at least one pig ent
(B) 10 biε 40 Gew.-% mindestens eineε oberflächenaktiven Additivε aus der Gruppe der nichtionischen Polyether und ihrer εauren Phoεphorεäure-, Phosphonsäure-, Schwefelsäure- und/oder Sulfonεäureester und deren Salzen(B) 10 to 40% by weight of at least one surface-active additive from the group of the nonionic polyethers and their acidic phosphoric, phosphonic, sulfuric and / or sulfonic esters and their salts
enthalten, zur Einfärbung von Kunststoffen.included, for coloring plastics.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Pigmentzubereitungen alε Komponente (B) indeεtens ein Additiv auε der Gruppe der Alkylenoxidblockcopolymere, der U εet- zungεprodukte von Alkylenoxiden mit Alkoholen, Aminen, ali- phatischen Carbonεäuren oder Carbonεäureamiden, der sauren Phosphorεäure-, Phosphonsäure-, Schwefelsäure- und Sulfon- säureeεter dieser Alkylenoxidverbindungen und der Salze die- εer Ester enthalten.2. Use according to claim 1, characterized in that the pigment preparations as component (B) an additive from the group of alkylene oxide block copolymers, the reaction products of alkylene oxides with alcohols, amines, aliphatic carboxylic acids or carboxylic acid amides, the acidic phosphoric acid, , Phosphonic acid, sulfuric acid and sulfonic acid esters of these alkylene oxide compounds and the salts of these esters.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Pigmentzubereitungen in Form von Granulaten mit einer mittleren Korngröße von 50 bis 5000 μm und einer BET-Oberflache von < 15 m2/g vorliegen.3. Use according to claim 1 or 2, characterized in that the pigment preparations are in the form of granules having an average grain size of 50 to 5000 microns and a BET surface area of <15 m 2 / g.
4. Verwendung nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Kunststoffe abgewandelte Naturstoffe oder εyn- thetische Kunstεtoffe εind.4. Use according to claims 1 to 3, characterized in that the plastics are modified natural materials or synthetic synthetic materials.
5. Verwendung nach den Anεprüchen 1 biε 4, dadurch gekennzeich- net, daß die Kunststoffe thermoplastische Kunststoffe auf der5. Use according to claims 1 to 4, characterized in that the plastics are thermoplastics on the
Baεis von Polyolefinen oder PolyvinylVerbindungen sind.Are based on polyolefins or polyvinyl compounds.
6. Verfahren zur Einfärbung von Kunεtstoffen, dadurch gekennzeichnet, daß man feste Pigmentzubereitungen gemäß den An- εprüchen 1 biε 3 durch Extrudieren, Walzen, Kneten oder Mahlen in die Kunststoffe einarbeitet. 6. A process for coloring plastics, characterized in that solid pigment preparations according to claims 1 to 3 are incorporated into the plastics by extrusion, rolling, kneading or grinding.
PCT/EP2003/007591 2002-07-19 2003-07-14 Use of solid pigment preparations for colouring plastics WO2004009688A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003250052A AU2003250052A1 (en) 2002-07-19 2003-07-14 Use of solid pigment preparations for colouring plastics

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002133081 DE10233081A1 (en) 2002-07-19 2002-07-19 Use of solid pigment preparations for coloring plastics
DE10233081.6 2002-07-19

Publications (2)

Publication Number Publication Date
WO2004009688A2 true WO2004009688A2 (en) 2004-01-29
WO2004009688A3 WO2004009688A3 (en) 2004-07-22

Family

ID=30010268

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/007591 WO2004009688A2 (en) 2002-07-19 2003-07-14 Use of solid pigment preparations for colouring plastics

Country Status (3)

Country Link
AU (1) AU2003250052A1 (en)
DE (1) DE10233081A1 (en)
WO (1) WO2004009688A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005019431A1 (en) * 2005-04-25 2006-10-26 Eckart Gmbh & Co. Kg Non-dusty powder pigment composition, useful in e.g. printing colors and varnishes, comprises a radiant pearl pigment, nonionic monomer crosslinking agent and/or nonionic polysiloxane based crosslinking agent and a solvent
US8334386B2 (en) 2007-07-03 2012-12-18 Basf Se Aqueous synthesis of perylene pigments

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10253804A1 (en) 2002-11-18 2004-05-27 Basf Ag Solid pigment preparation for use with high mol. wt. (in)organic materials contains a polymeric water-soluble anionic surfactant and optionally also a polyether- based nonionic surfactant
DE10256416A1 (en) 2002-12-02 2004-06-09 Basf Ag Solid pigment preparations containing pigment derivatives and surface-active additives
DE102005005846A1 (en) * 2005-02-08 2006-08-17 Basf Ag Solid pigment preparations containing water-soluble polyurethane-based surface-active additives
DE102005005975A1 (en) * 2005-02-09 2006-08-31 Basf Ag Solid pigment preparations containing fillers and water-soluble surface-active additives
DE102005020742A1 (en) * 2005-05-02 2006-03-30 Basf Ag Use of solid pigment preparation (comprising pigment and water-soluble surface-active additive) for coloring cellulose/polymer composite materials
DE102012013046A1 (en) 2012-06-29 2014-01-02 Clariant International Ltd. Fatty acid condensation products as dispersants in pigment preparations

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1499660A (en) * 1974-10-26 1978-02-01 Ciba Geigy Ag Pigment compositions
DE3132303A1 (en) * 1981-08-17 1983-02-24 Bayer Ag, 5090 Leverkusen Preparation of low-dusting inorganic pigment granules having a narrow particle size distribution
US4464203A (en) * 1981-12-29 1984-08-07 Basf Aktiengesellschaft Highly concentrated, dust-free, solid and readily dispersible pigment formulations and their use
DE19905269A1 (en) * 1999-02-09 2000-08-10 Bayer Ag Solid pigment preparations
EP1081195A2 (en) * 1999-08-28 2001-03-07 Clariant GmbH Process for the manufacture of pigment granules
WO2003064540A1 (en) * 2002-02-01 2003-08-07 Basf Aktiengesellschaft Granular pigment
WO2004000903A1 (en) * 2002-06-20 2003-12-31 Basf Aktiengesellschaft Solid pigment preparations containing anionic and non-ionic surface-active additives

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1499660A (en) * 1974-10-26 1978-02-01 Ciba Geigy Ag Pigment compositions
DE3132303A1 (en) * 1981-08-17 1983-02-24 Bayer Ag, 5090 Leverkusen Preparation of low-dusting inorganic pigment granules having a narrow particle size distribution
US4464203A (en) * 1981-12-29 1984-08-07 Basf Aktiengesellschaft Highly concentrated, dust-free, solid and readily dispersible pigment formulations and their use
DE19905269A1 (en) * 1999-02-09 2000-08-10 Bayer Ag Solid pigment preparations
EP1081195A2 (en) * 1999-08-28 2001-03-07 Clariant GmbH Process for the manufacture of pigment granules
WO2003064540A1 (en) * 2002-02-01 2003-08-07 Basf Aktiengesellschaft Granular pigment
WO2004000903A1 (en) * 2002-06-20 2003-12-31 Basf Aktiengesellschaft Solid pigment preparations containing anionic and non-ionic surface-active additives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005019431A1 (en) * 2005-04-25 2006-10-26 Eckart Gmbh & Co. Kg Non-dusty powder pigment composition, useful in e.g. printing colors and varnishes, comprises a radiant pearl pigment, nonionic monomer crosslinking agent and/or nonionic polysiloxane based crosslinking agent and a solvent
US8334386B2 (en) 2007-07-03 2012-12-18 Basf Se Aqueous synthesis of perylene pigments

Also Published As

Publication number Publication date
AU2003250052A8 (en) 2004-02-09
WO2004009688A3 (en) 2004-07-22
DE10233081A1 (en) 2004-02-05
AU2003250052A1 (en) 2004-02-09

Similar Documents

Publication Publication Date Title
EP1565531B1 (en) Solid pigment preparations containing water-soluble anionic surface-active additives that comprise carboxylate groups
EP0257423B1 (en) Hydrophobic pigments and fillers for incorporation into plastics
EP1570006B1 (en) Solid pigment preparations containing pigment derivatives and surface-active additives
DE19649756B4 (en) Process for the preparation of briquetting and pressed granules from carbon black pigments and their use
DE69712165T2 (en) Manufacturing process of a pigment composition
EP1913095B1 (en) Solid pigment preparations containing water-soluble surface-active additives and anti-oxidants
EP2159266B1 (en) Pigment granulates containing inorganic filter aids
DE112006000180B4 (en) Solid pigment preparations containing water-soluble polyurethane-based surface-active additives, processes for their preparation and their use
EP1845137B1 (en) Method for manufacturing pigment pellets and their application
DE10204304A1 (en) pigment granules
WO2003066743A1 (en) Pigment preparations
DE102005005975A1 (en) Solid pigment preparations containing fillers and water-soluble surface-active additives
DE10054344A1 (en) Use of coated pigment granules in electrophotographic toners and developers, powder coatings and ink-jet inks
EP2046898A1 (en) Pigments modified by a polymerisable coating, and production and use of same
EP2234708B1 (en) Production of a solid pigment preparation in the form of granules by spray drying
WO2004009688A2 (en) Use of solid pigment preparations for colouring plastics
EP1546264A1 (en) Solid pigment preparations comprising surface active additives based on alkoxylated bisphenols
EP0028713B1 (en) Matting agent for varnishes based on wax, process for its production, and matted varnishes
EP1004616B1 (en) Micronized polyolefins for preparing pigment concentrates
EP1339802B1 (en) Method for producing dust-free, pourable pigment concentrations
DE10204583A1 (en) Pigment composition, useful in paints, inks and building materials, comprises a pigment, a non-ionic polyether based surfactant and an anionic sulfonate, sulfate, phosphonate or phosphate based surfactant
EP2265678B1 (en) Solid silicic acid preparation
EP1478698A1 (en) Moist granulates of organic pigments, method for the production thereof, and use thereof
WO2008012245A2 (en) Pigment preparations in pellet form
DE10314519A1 (en) Granular dye preparation, used in paper, paper coating, paint, lacquer, printing ink, building material, film, fibers, textile, dental material, plastics or polymer composite, contains crosslinked polymer or block copolymer as binder

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP