US20210107803A1 - Iron oxide pigments containing al - Google Patents

Iron oxide pigments containing al Download PDF

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US20210107803A1
US20210107803A1 US16/498,511 US201816498511A US2021107803A1 US 20210107803 A1 US20210107803 A1 US 20210107803A1 US 201816498511 A US201816498511 A US 201816498511A US 2021107803 A1 US2021107803 A1 US 2021107803A1
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iron
aluminium
ions
pigments
sulfate
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Kai BUETJE
Christine Kathrein
Carsten Rosenhahn
Juergen Kischkewitz
Ulrich Meisen
Koehler KOEHLER
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Lanxess Deutschland GmbH
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Priority claimed from EP17164231.7A external-priority patent/EP3381984A1/de
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0045—Mixed oxides or hydroxides containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C01P2006/13—Surface area thermal stability thereof at high temperatures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65—Chroma (C*)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the invention relates to new Al-containing iron oxide pigments, to a process for producing them and to their use for the colouring of pastes, paints, plastics, paper and building materials.
  • High-grade red iron oxide pigments which represent the state of the art are customarily single-phase haematites having Fe 2 O 3 contents of 96.5 wt % up to 99.5 wt %.
  • Processes possessing particular industrial significance are the Copperas, precipitation and Penniman processes and also the calcining of iron oxide precursors based on goethite and magnetite.
  • red pigments Important fields for use of these red pigments are inks and paints (solventborne, aqueous and powder coatings), plastics, and also paper and laminates, with levels of pigmentation of up to around 35 wt %.
  • red iron oxide pigments For measuring the colour properties of red iron oxide pigments, there are long-established test methods, in which the colouredness of media coloured using red iron oxide pigments, such as test specimens of plastic or paint systems, is measured.
  • Standard parameters established for measuring the colouredness of red iron oxide pigments include the parameters of what is called the CIELAB colour space.
  • CIELAB colour space every perceptible colour within this three-dimensional colour space is defined by the colour locus with the coordinates L* (lightness), a* (red-green value) and b* (yellow-blue value).
  • L* lightness
  • a* red-green value
  • b* yellowness of the colour.
  • the colour blue in contrast, becomes stronger as the b* value becomes more negative.
  • the saturation C ab * also called chroma, or chromaticity
  • This value is a direct product of the values a* and b* and represents the square root of the sum of the squares of a* and b*.
  • the values a*, b*, L*, and C ab * are dimensionless values which are commonly identified as “CIELAB units”.
  • the corresponding colorimetry in plastics takes place, for example, in polyethylene (high-density polyethylene, HDPE) at a level of pigmentation of 1 wt %.
  • polyethylene high-density polyethylene, HDPE
  • DE 3500470 attempted to use the precipitant MgO and a specific precipitation methodology in order to provide an Al-doped haematite having an improved hue (see Examples 7 and 8). While it did find as light increase in the b* value (see Comparative Example Bversus A), as a result of using MgO as against NaOH in the Al-free haematite, the absolute colour values found in DE'470 even for the A-doped haematites were still in need of improvement, especially the b* values. In any case, the presence of magnesium leads to the formation of Mg ferrites, which do not have good coloristic qualities.
  • a comparison of MgO and the variant addition described in EP'331 relative to the procedure of the present invention can be found in Comparative Example III of the present invention (for results see Table 1).
  • Al-containing red iron oxide pigments are produced by coating of finely divided goethite ( ⁇ -FeOOH) precursors with aluminium compounds, with subsequent calcination.
  • ⁇ -FeOOH finely divided goethite
  • the reworking, for example, of Example 3 in that specification yielded Al-containing red iron oxide pigments whose colour properties, however, are still in need of improvement (Tab. 1).
  • red pigments which expand the colour space relative to the red iron oxide pigments in the prior art.
  • These new pigments are preferably to possess a higher saturation C ab * as well and, in particular, an improved heat stability, in plastics, for example. It has been found that specific Al-containing iron oxide pigments achieve this object.
  • the invention therefore relates to Al-containing iron oxide pigments of the formula Fe 2-x Al x O 3 with x values from 0.01 to 0.25, characterized in that they possess an a* value of 30.5 to 32.5 CIELAB units and a b* value of 25.5 to 30.5 CIELAB units, measured in each case in the alkyd resin according to DIN EN ISO 787-25: 2007 as full shade.
  • the Al-containing iron oxide of the invention is preferably present in a haematite structure.
  • the aluminium is located preferably at the octahedral lattice sites in substitution of Fe 3+ ions.
  • Preferred Al-containing iron oxides have a saturation C ab * of 39.8 to 44.6 CIELAB units.
  • C ab * here represents the square root of the sum of the squares of a* and b*, measured in the varnish system above.
  • the pigments of the invention preferably possess a heat stability measured in HDPE polyethylene at 1% pigmentation, determined according to DIN EN 12877-2 by a change ( ⁇ C ab *) in the saturation (C ab *) of less than 3 CIELAB units, preferably less than 1.5 CIELAB units, on temperature increase from 200 to 320° C.
  • the Al index x is a number from 0.01 to 0.10, more particularly from 0.025 to 0.075.
  • pigments of the invention in which, in the formula, the Al index x is a number from 0.11 to 0.25, more particularly from 0.12 to 0.15.
  • the pigments of the invention likewise preferably have a water content of less than 0.8 wt %, preferably of less than 0.5 wt %.
  • the pigments of the invention have a chloride content of less than 0.1 wt %, preferably less than 0.01 wt %, based on the pigment.
  • the amount of manganese and chromium as well is preferably very small.
  • the sum total of manganese and chromium is preferably less than 500 ppm, very preferably less than 100 ppm, based on the pigment.
  • the amount of magnesium is preferably less than 500 ppm, very preferably less than 100 ppm, based on the pigment.
  • the pigments of the invention preferably have a specific surface area by the BET method of 6.5 to 12.5 m 2 /g.
  • the pigments of the invention may also be coated. In that case they may have one or more coatings selected from organic and/or inorganic compounds.
  • Organic coating materials include, for example, polyhydric alcohols, polyethylene glycols, polypropylene glycols, their etherification products with monohydric alcohols and esterification products with carboxylic acids, and also silicone oils.
  • Suitable inorganic coating materials are preferably colourless oxides or hydroxides of Al, Si, Zr and Mg, especially Al 2 O 3 .
  • the coating materials are employed preferably in an amount of 0.01 to 3 wt %, based on the pigment.
  • the invention further relates to a process for producing the pigments of the invention, comprising at least the steps of a) precipitation, b) oxidation and c) calcination, characterized in that:
  • the Fe:Al ratio of 199:1 to 7:1 corresponds, in the target composition of Fe 2-x Al x O 3 , to an x value of 0.01 to 0.25.
  • the aqueous solution comprising ions of iron, of sulfate and of aluminium can be obtained by mixing corresponding sulfate-containing iron salt solutions with solutions containing aluminium ions, which in turn may be obtained individually from corresponding iron precursors and aluminium compounds, respectively.
  • iron(II) sulfates for such iron sulfate solutions can be obtained from steel-pickling plants or from TiO 2 production by the sulfate process, or by dissolving metallic iron, iron carbonates, iron hydroxides or iron oxides in sulfuric acid.
  • iron(II) sulfate solutions having a total iron content of 80 to 95 g/I and a sum content of manganese and chromium of less than 250 mg/I.
  • the solution used preferably also includes a magnesium content of less than 500, preferably less than 100 ppm, based on the solution.
  • Preferred for the precipitation according to step a) is an aqueous solution comprising ions of iron, of sulfate and aluminium in which the iron ions are present in the form of a mixture of iron(II) and iron(III) ions, preferably with an Fe(III) fraction of 5 to 30 mol %, more particularly 10 to 20 mol % Fe(III), based on the total amount of iron in the solution.
  • Setting the correspondingly preferred Fe(III) fractions in the respective iron(II)/(III) sulfate mixture can be done either by adding corresponding amounts of iron salts, preferably of iron(III) sulfate, or by partial oxidation of the iron salt solution, preferably the iron(II) sulfate solution, with—for example—atmospheric oxygen, preferably at temperatures of 80° C. or above, in particular at 80 to 100° C., or with H 2 O 2 at temperatures preferably of 20 to 70° C.
  • Al components used in the aqueous solution comprising ions of iron, of sulfate and of aluminium may be aluminium salts such as, for example, chlorides, sulfates or else nitrates, particular preference being given to Al(III) sulfates.
  • the aqueous solution comprising ions of iron, of sulfate and of aluminium for step a1) preferably contains a molar ratio of iron in the form of Fe(II) and/or Fe(III) to Al ions of 79:1 to 26:1, preferably of 17.2:1 to 7:1, more particularly of 15.7:1 to 12.3:1.
  • An Fe:Al ratio of 79:1 to 26:1 here corresponds, in the target composition Fe 2-x Al x O 3 , to an x value of 0.025 to 0.075; an Fe:Al ratio of 17.2:1 to 7:1 here corresponds to an x value of 0.11 to 0.25; and an Fe:Al ratio of 15.7:1 to 12.3:1 here corresponds to an x value of 0.12 to 0.15.
  • aqueous solutions comprising ions of iron, of sulfate and of aluminium and used in accordance with the invention are provided preferably by mixing of the Fe(III)- and/or Fe(II)-containing sulfate solution and of corresponding Al-containing solutions.
  • the reaction in step a1) is preferably accomplished by heating the alkaline compound as precipitant in a suitable reaction vessel with stirrer, gasification container and electrical heating to the reaction temperature.
  • the reaction temperature is preferably 20 to 100° C., more particularly 80 to 100° C., more preferably 85 to 100° C.
  • the aqueous solution comprising ions of iron, of sulfate and of aluminium is metered into the initial charge of the alkaline compound, preferably in the form of its aqueous solution. This addition is preferably made at the reaction temperature.
  • the precipitation here takes place preferably at a pH of greater than 10, more particularly at a pH of 10.5 to 14.
  • the addition is made preferably with stirring. If a particular ratio of Fe(II) and Fe(III) has already been set in the aqueous solution comprising the ions of iron, of sulfate and of aluminium, it is preferred to allow the precipitation reaction to proceed under inert gas. Optionally, however, the Fe(II)/(III) ratio may also be set only during the precipitation, by means of the above-described oxidation.
  • the amount of alkaline compound to be used for the precipitation is a product of the amounts of the iron ions and aluminium ions, preference being given to a molar ratio of Fe total to OH ⁇ of 0.45 to 0.55 and also of Al(III) to OH ⁇ of 0.33, and also, optionally, of free acid present that is to be neutralized—sulfuric acid, for example.
  • the procedure and the proportions of the iron ions to aluminium ions are fundamentally the same as in the case of the precipitation a1), with the difference being that the aluminium compound is not present in the iron(II)/(III) sulfate mixture but is instead introduced as an initial charge together with the alkaline compound serving as precipitant.
  • the aluminium compound is preferably, for example, an aqueous Na aluminate solution which is mixed with the alkaline precipitant in order then to furnish the soluble Al ions.
  • Suitable alkaline compounds serving as precipitant are those specified under a1).
  • the alkaline precipitant is preferably included as an initial charge mixed with an alkali metal aluminate solution, and the iron(II)/(III) sulfate mixture is metered into this initial charge.
  • the precipitation is followed by oxidation with an oxidizing agent.
  • the oxidizing agent used is preferably an oxygen-containing gas, such as air, for example. This oxidation takes place preferably in the aqueous medium obtained after step a1) or a2), more particularly in the suspension obtained as a result of the precipitation.
  • the oxidizing agent, more particularly the oxygen-containing gas is preferably introduced into the aqueous medium obtained after step a1) or a2).
  • the oxidation according to step b) here takes place in particular at a temperature of 20 to 100° C. more particularly at 80 to 100° C. very preferably at 85 to 100° C.
  • the course of the oxidation and also the end of the oxidizing step can be checked, for example, by an EMF measurement using a commercial redox electrode in the reaction vessel.
  • the depletion of dissolved iron(II) ions in the reaction mixture is indicated by a jump in potential.
  • the pigment precursor preferably the magnetite formed
  • the filtrate conductivity is below 2000 ⁇ S/cm, preferably below 800 ⁇ S/cm, more preferably below 200 ⁇ S/cm. This is followed preferably by drying of the filter cake, in particular at a temperature of 30 to 250, preferably of 30 to 120° C.
  • the production of the Al-containing iron oxide pigments of the invention with the composition Fe 2-x Al x O 3 is accomplished by calcination of the oxidation product obtained after step b), preferably in the form of the isolated, washed and dried filter cake, also referred to as Al-containing magnetite, at a temperature of 500 to 1100° C., preferably of 600 to 975° C., preferably in the presence of an oxygen-containing gas, more particularly of air.
  • the level of optimum calcining temperature is dependent on the Al content of the oxidation product obtained after step b).
  • the optimum calcining temperature here is the temperature at which the maximum a* value (red fraction) has been obtained. This may be determined in a series of different calcining temperatures.
  • the pigments of the invention obtained after step c) may additionally be subjected to grinding and/or to coating.
  • inorganic coating it is preferred for coating to follow step c).
  • Preferred inorganic coating materials that are suitable are preferably colourless oxides or hydroxides of Al, Si, Zr and Mg, especially Al 2 O 3 .
  • Al-containing iron oxides of the invention with or without inorganic coating, to be subjected additionally to milling.
  • Suitable milling methods are, for example, jet milling, pendulum milling or else wet milling operations.
  • organic coating materials examples being polyhydric alcohols, polyethylene glycols, polypropylene glycols, their etherification products with monohydric alcohols and esterification products with carboxylic acids, and also silicone oils. These coating materials may likewise act as milling assistants.
  • the preferred quantities of coating materials for metered addition may be from 0.01 to 3 wt % in the case of inorganic coating materials and from 0.01 to 1 wt % in the case of organic coating materials.
  • the sum total of organic and inorganic coating materials in this context is 0.01 to 3 wt %.
  • the invention further relates to the use of the pigments of the invention for colouring pastes, paints, plastics, paper and building materials.
  • a thixotroped long-oil alkyd resin (WorléeKyd P 151) were applied to the bottom part of a plate paint dispersion machine (TFAM) with a plate diameter of 240 mm, and the red iron oxide pigment in question was processed with the test paste to form a coloured paste with a PVC (pigment volume concentration) of 10%.
  • TFAM plate paint dispersion machine
  • the test paste contains 95 wt % of alkyd resin (Worléekyd P 151 from Worlée-Chemie GmbH, DE) and 5 wt % of Luvotix HAT thixotropic agent (Lehmann & Voss & Co KG, DE).
  • the Luvotix is incorporated by stirring into the alkyd resin which has been preheated at 70 to 75° C., and the mixed paste is heated at 95° C. until dissolution has taken place. After cooling, the paste is rolled free of bubbles on a triple-roll mill.
  • the red pigments were weighed out according to
  • m P mass of red iron oxide pigment
  • PVC pigment volume concentration
  • m b mass of binder
  • ⁇ p density of pigment
  • ⁇ b density of binder
  • the completed paste was transferred to a paste plate and subjected to colorimetry on a Datacolor 600 colorimeter with the measuring geometry of d/8° and the illuminant D65/10° with gloss (CIELAB colour space according to DIN 5033 Part 7 ).
  • HDPE polyethylene
  • the same red pigment was processed in HD-PE and the heat stability was ascertained by measurement of the saturation C ab * as a function of the processing temperature between 200 and 320° C. (see Table 6 and FIG. 1 ).
  • the oxidation time was around 10.5 hours at 85° C.
  • the oxidation product was calcined in a chamber kiln at the optimum calcining temperature of 900° C. (accuracy ⁇ 5° C.) in a residence time of 30 minutes under an oxidizing atmosphere. To determine the optimum calcining temperature, a variety of temperatures were trialled (see Table 3).
  • the inventive pigment obtained was characterized—as indicated in Table 4—and tested coloristically in WorléeKyd P 151 (full shade) (for colorimetric values see Table 5).
  • This oxidation product was calcined at the optimum calcining temperature of 700° C. (accuracy ⁇ 5° C.) with a residence time of 30 minutes in an oxidizing atmosphere in a chamber kiln.
  • optimum calcining temperature 700° C. (accuracy ⁇ 5° C.) with a residence time of 30 minutes in an oxidizing atmosphere in a chamber kiln.
  • a variety of temperatures were trialled (see Table 3).
  • inventive Al-containing pigments from Inventive Examples 1 (0.81% Al) and 2 (2.2% Al) represent high-grade Al-containing red iron oxide pigments having specific surface areas by the BET method in the range from 8.6 to 9.6 m 2 /g and they exhibit very high chemical purity, characterized by Mn and Cr contents of in total below 100 ppm, by C contents of below 250 ppm and by low H 2 O contents of less than 0.01 wt % (see Table 5).
  • the inventive Al-containing red pigments are characterized by a significantly higher heat stability in HD-PE (as ⁇ C ab * values of 200 versus 320° C., see Table 6) with a significantly higher saturation C ab *, specifically:
  • the noninventive pigment obtained was characterized—as indicated in Table 4—and tested coloristically in WorléeKyd P 151 (full shade) (for colorimetric values see Table 5).
  • Inventive Example 1 was repeated, but using MgO rather than NaOH as precipitant, in half the molar quantity in accordance with the divalent nature of Mg, as employed for the production of Al-doped iron oxide in Example 7 of EP-A-187331.
  • the initial charge, rather than the NaOH was the Fe(II)/Fe(III)/Al(III) sulfate mixture, and the MgO precipitant was added to this initial charge likewise as described in EP'331. Accordingly, the differences of a different precipitant and a different sequence of addition were transposed from EP'331 to Inventive Example 1 of the invention.
  • the pigment produced was measured in analogy to the determination of colour data for the inventive examples above.
  • the noninventive pigment obtained was characterized—as indicated in Table 4—and tested coloristically in WorléeKyd P 151 (full shade) (for colorimetric values see Table 5).
  • the optimum calcining temperature is highlighted by bold text.

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  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
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US16/498,511 2017-03-31 2018-03-19 Iron oxide pigments containing al Abandoned US20210107803A1 (en)

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EP17164231.7 2017-03-31
EP17164231.7A EP3381984A1 (de) 2017-03-31 2017-03-31 Al-haltige eisenoxidpigmente
EP17179589.1 2017-07-04
EP17179589 2017-07-04
EP18155087.2 2018-02-05
EP18155087 2018-02-05
PCT/EP2018/056863 WO2018177789A1 (de) 2017-03-31 2018-03-19 Al-haltige eisenoxidpigmente

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DE2826941C2 (de) 1978-06-20 1985-11-21 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Eisenoxidrotpigmenten
DE3124746A1 (de) * 1981-06-24 1983-01-13 Basf Ag, 6700 Ludwigshafen Plaettchenfoermige pigmente der formel al(pfeil abwaerts)x(pfeil abwaerts)fe(pfeil abwaerts)2(pfeil abwaerts)-(pfeil abwaerts)x(pfeil abwaerts)o(pfeil abwaerts)3(pfeil abwaerts), deren herstellung und verwendung
JPS582226A (ja) * 1981-06-29 1983-01-07 Tone Sangyo Kk 赤色酸化鉄の製造方法
DE3500470A1 (de) * 1985-01-09 1986-07-10 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung heller farbreiner eisenoxidrotpigmente
DE3716300A1 (de) * 1987-05-15 1988-11-24 Bayer Ag Neue farbreine eisenoxidpigmente, verfahren zu ihrer herstellung und deren verwendung
CN1106036A (zh) * 1994-01-26 1995-08-02 拜尔公司 纯色氧化铁直接红颜料的制法和用途
DE59605913D1 (de) * 1995-10-26 2000-10-26 Bayer Ag Farbreine, gelbstichige Eisenoxidrotpigmente, Verfahren zu ihrer Herstellung sowie deren Verwendung
JPH11102238A (ja) * 1997-09-29 1999-04-13 Toshiba Corp コンピュータシステムおよびそのシステムにおけるサスペンド制御方法
DE19746262A1 (de) * 1997-10-20 1999-04-22 Bayer Ag Eisenoxidrotpigmente, Verfahren zur Herstellung von Eisenoxidrotpigmenten und deren Verwendung
JP3728505B2 (ja) * 2002-07-09 2005-12-21 国立大学法人 岡山大学 Ａｌ置換ヘマタイトの製造方法
DE102004024013A1 (de) 2004-05-14 2005-12-01 Bayer Chemicals Ag Farbreine, gut dispergierbare Eisenoxidrotpigmente mit hoher Mahlstabilität
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JP6388104B2 (ja) * 2013-11-01 2018-09-12 戸田工業株式会社 酸化鉄粒子粉末、該酸化鉄粒子粉末を用いた塗料及び樹脂組成物
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JP7038995B2 (ja) * 2016-10-21 2022-03-22 国立大学法人 岡山大学 赤色顔料用及び触媒用酸化鉄並びにその製造方法

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AU2018246923B2 (en) 2020-04-09
CN110506081A (zh) 2019-11-26
BR112019020265A2 (pt) 2020-04-22
WO2018177789A1 (de) 2018-10-04
EP3601439B1 (de) 2021-03-03
KR20190141131A (ko) 2019-12-23
US20220259064A1 (en) 2022-08-18
MX2019011586A (es) 2019-11-08
JP2020515686A (ja) 2020-05-28
JP6935505B2 (ja) 2021-09-15
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AU2018246923A1 (en) 2019-11-14
KR102476176B1 (ko) 2022-12-12

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