EP2758477A1 - Procédé de modification de surface de pigments de dioxyde de titane - Google Patents

Procédé de modification de surface de pigments de dioxyde de titane

Info

Publication number
EP2758477A1
EP2758477A1 EP12780410.2A EP12780410A EP2758477A1 EP 2758477 A1 EP2758477 A1 EP 2758477A1 EP 12780410 A EP12780410 A EP 12780410A EP 2758477 A1 EP2758477 A1 EP 2758477A1
Authority
EP
European Patent Office
Prior art keywords
pigment
titanium dioxide
particles
surface coating
weight
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP12780410.2A
Other languages
German (de)
English (en)
Inventor
Uwe WILKENHÖNER
Jürgen Bender
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kronos International Inc
Original Assignee
Kronos International Inc
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 Kronos International Inc filed Critical Kronos International Inc
Publication of EP2758477A1 publication Critical patent/EP2758477A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C09C1/36—Compounds of titanium
    • C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • 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
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • 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
    • C01P2006/62—L* (lightness 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)

Definitions

  • the invention relates to a process for the surface modification of titanium dioxide pigment and to the use of the titanium dioxide pigment in particular in paints for interior and exterior walls (emulsion paints) and in water-based paints.
  • Titanium dioxide is generally the most important white pigment in the application fields of paints and coatings, plastics, paper and fibers because of its high refractive index.
  • the optical properties e.g. Lightening power, hue or opacity Photostability
  • the titanium dioxide pigment particles therefore become
  • Paints for interior and exterior walls usually contain titanium dioxide pigment in addition to significant amounts of so-called
  • Extenders for example calcium carbonate, diatomaceous earth or barium sulfate.
  • the extenders have the task of keeping the pigment particles separated in color, so that as far as possible every single pigment particle can be optically active. In this way high values can be obtained for the total pigment (plus extender) volume concentration of 70% and more.
  • Titanium dioxide pigments for use in emulsion paints must on the one hand have high hiding power (opacity) and, on the other hand, good dispersibility. To achieve the high hiding power, they are usually provided with a voluminous, porous, loose coating of silicon and aluminum oxide.
  • the voluminous, loose structure of the surface coating acts as a spacer between the individual particles and leads via the dry-hiding effect to increased hiding power.
  • the porous surface coating of the pigment affects the
  • the invention is based on the object of specifying a method with which a
  • Titanium dioxide pigment can be prepared, which performs the tasks of a part of the additives in emulsion paints, in particular the optimization of theological behavior (e.g., viscosity) and open time of the paint.
  • theological behavior e.g., viscosity
  • the object is achieved by a method for surface modification of
  • the particles are first provided with an inorganic surface coating, which has a loose structure and
  • the particles are subsequently subjected to high shear and impact forces, so that the loose structure of the inorganic surface coating is at least partially compressed.
  • the loose structure of the surface coating is subsequently compacted by the action of mechanical energy.
  • the invention relates to a process for the surface modification of titanium dioxide pigment, whereby the open time and viscosity of the emulsion paint prepared therewith are influenced in parallel so that, for example, the open time of the ink remains constant
  • Viscosity is prolonged or the viscosity of the ink is increased while the open time remains the same.
  • the invention is based on a titanium dioxide pigment, which with silica and / or
  • Alumina was coated with a looser structure, hereinafter referred to as "starting pigment.”
  • starting pigment a looser structure
  • the total amount of the precipitated coating substances in the starting pigment is preferably at least 10% by weight calculated as the oxide and based on the total pigment.
  • the silicon oxide content is preferably 5 to 20 wt .-% and the alumina content is preferably from 0.5 to 8 wt .-% based on the total pigment.
  • the specific surface area (according to BET) of the starting pigment is preferably about 40 to 80 m 2 / g.
  • the oil number of the starting pigment (measured according to DIN EN ISO 787-5) is preferably about 20 to 80 g / 100g pigment.
  • the bulk density of the pigment is preferably about 0.4 to 0.7 g / cm 3 .
  • the starting pigment is surface-modified by being exposed in a suitable device to high shear and impact forces, preferably in a device of the stator / rotor type.
  • a suitable device to high shear and impact forces
  • a device of the stator / rotor type preferably a mixing container with
  • the mixing container may be e.g. a drum with rotating mixing tools or a rotating drum with fixed or rotating mixing tools act.
  • Rotational movement of the mixing container can be described by the dimensionless Froude number.
  • the dimensionless Froude number Fr P is defined as the ratio of centrifugal force FZ to gravitational force F, which act on the individual particle (P), ie
  • the Froude number correlates with the speed of the rotor.
  • the particle movement in the mixing container with the so-called Frough tool number Fr w can be described, ie
  • the tool Froudeiere Fr w is preferably at values of about> 10, in particular about> 30 and preferably about> 100.
  • the specific energy input (based on the pigment mass) in the surface modification of the starting pigment is between 1 and 10000 kJ / kg, in particular between 10 and 5000 kJ / kg and preferably between 100 and 2000 kJ / kg.
  • the apparatus used according to the invention for surface modification of the starting pigment is operated at a peripheral rotor speed of 0.1 to 100 m / s, preferably at a peripheral rotor speed of 5 to 50 m / s.
  • the process time for the surface modification of the starting pigment can vary over wide limits.
  • the process time varies in the range of 0.5 to 100 minutes, more preferably 1 to 30 minutes, and preferably 2 to 10 minutes.
  • the surface modification of the starting pigment according to the invention leads to a densification and / or to a substantial adhesion of the coating substances precipitated separately as flaky agglomerates to the surface of the pigment particles and furthermore to an at least partial densification of the surface of the pigment particles.
  • the surface-modified pigment according to the invention differs from that
  • the specific surface area (BET) of the starting pigment is reduced by up to about 30 to 40% with the aid of the process according to the invention.
  • the specific surface area (BET) of the starting pigment is reduced from greater than about 60 m 2 / g to less than about 40 m 2 / g.
  • the oil content (according to DIN EN ISO 787-5) of the starting pigment preferably changes from about 45 g of oil / 100 g of pigment to about 36 g of oil / 100 g of pigment.
  • a particular variant of the method described involves the use of organic substances with which the pigment can be coated during the treatment.
  • suitable organic additives By using suitable organic additives, the BET surface area and thus the oil number of the pigment treated with the described process can be further reduced.
  • the additives can be added in solid or in liquid form.
  • Particularly suitable here are hydrophobizing additives such as e.g. Waxes with or without further chemical functionalization, polyolefins or similar substances.
  • the (partial) hydrophobicity additionally causes the desired theological effects.
  • dispersing additives or other auxiliaries customary in coating technology can be used, for example, for rheology, defoaming, wetting, etc.
  • the amount of added organic additives is preferably 0.05 to 30 wt .-%, in particular 0.5 to 10 wt .-% based on the starting pigment.
  • the titanium dioxide pigment particles prepared according to the invention are particularly suitable for use in interior and exterior dispersion paints and in water-based paints
  • the starting pigment used was the pigment KRONOS 2044, a pigment aftertreated with a high amount of SiO 2 and Al 2 O 3 .
  • the starting pigment KRONOS 2044 has a loose surface coating of> 10% by weight of Si0 2 and> 3% by weight of Al 2 O 3 , the surface coating material being largely adjacent to the TiO 2 surface (FIG. 1, transmission electron micrograph).
  • the specific surface area (BET) of the KRONOS 2044 pigment is about 60 to 65 m 2 / g.
  • the oil count is about 45g / 100g pigment.
  • the pigment (about 300 g) was placed in the particle coater "Nobilta NOB-130" from Hosokawa Alpine and then subjected to a controlled shearing action.
  • the pigment was treated mechanically in the device.
  • Product temperature was limited to ⁇ 80 ° C by water cooling of the housing.
  • the process time was 3 to 5 minutes of intense shear. The in this process
  • Tool Froude numbers used were between 450 and 900.
  • the thus mechanically treated pigment had a BET specific surface area (BET) of 30 to 38 m 2 / g and an oil content of about 37 g / 100 g of pigment.
  • Picture 2 shows a
  • Acticid MBS Algicide / fungicide
  • Omyacarb 5-GU (filler) 15.50% by weight -%
  • Mowilith LDM 1871 (binder) 11.00% by weight
  • the test colors were each determined in terms of brightness L * (white), color cast b * (white),
  • the white internal emulsion paint (test color) prepared according to the recipe specification was applied to Morest cards by means of a film-drawing apparatus at a speed of 12.5 mm / s using a 300 ⁇ m doctor blade. The elevators were dried overnight at 23 ° C in the laboratory. The brightness L * (white) and the hue b * (white) of the white coating were measured with the spectrophotometer Color-view from Byk-Gardner.
  • the white internal dispersion paint (test color) prepared according to the formulation recipe was applied to Morest contrast maps at a rate of 12.5 mm / s using a 300 nm doctor blade by means of an automatic film applicator. Subsequently, the color values Y were against a black background (Y (SC hwarz)) and Y on a white background (Y (W hite)) were measured three times each with the spectrophotometer Color-view.
  • the contrast ratio was calculated according to the following formula:
  • a paint film of 300 .mu.m thickness was applied to a Morest badge by a step doctor and then determines the time in minutes to the drying of the paint film.
  • the paint film was considered “dried” as soon as it was tack-free and a fingerprint left no permanent mark.
  • the viscosity of the internal dispersion paint was measured using a Brookfield viscometer (model KU-2), indicated as Krebs Units (KU).
  • the specific surface area (BET) of the pigment was measured using a Tristar 3000 from the company.
  • the oil number of the pigment was determined in accordance with DIN EN ISO 787-5.
  • starting pigments (FIG. 1) and the starting pigment treated according to the invention (FIG. 2) clearly show that the loose coating of the particles by the mechanical treatment according to the invention to a great extent on the

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé de modification de surface de pigments de dioxyde de titane et son utilisation en particulier dans des matériaux de revêtement, pour des parois intérieures et extérieures (peintures en dispersion) et dans des systèmes de peinture à base d'eau. A l'aide des pigments selon la présente invention, le comportement rhéologique et le temps d'ouverture des peintures peuvent être optimisés. Le procédé de modification de surface concerne des pigments de dioxyde de titane qui ont été pourvus d'un revêtement de surface à structure lâche et soumet ensuite les particules de pigments à des forces de cisaillement et d'impact élevées, de telle sorte que la structure lâche du revêtement de surface est au moins en partie comprimée. Les particules de pigments sont de préférence revêtues d'oxyde de silicium et/ou d'oxyde d'aluminium. La surface spécifique (BET) est réduite d'environ 30 % par l'intermédiaire du procédé selon la présente invention.
EP12780410.2A 2011-09-22 2012-09-19 Procédé de modification de surface de pigments de dioxyde de titane Withdrawn EP2758477A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011113896A DE102011113896A1 (de) 2011-09-22 2011-09-22 Verfahren zur Oberflächenmodifizierung von Titandioxidpigment
PCT/EP2012/003903 WO2013041217A1 (fr) 2011-09-22 2012-09-19 Procédé de modification de surface de pigments de dioxyde de titane

Publications (1)

Publication Number Publication Date
EP2758477A1 true EP2758477A1 (fr) 2014-07-30

Family

ID=47115712

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12780410.2A Withdrawn EP2758477A1 (fr) 2011-09-22 2012-09-19 Procédé de modification de surface de pigments de dioxyde de titane

Country Status (4)

Country Link
US (1) US20130074734A1 (fr)
EP (1) EP2758477A1 (fr)
DE (1) DE102011113896A1 (fr)
WO (1) WO2013041217A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016003526A1 (de) 2016-03-22 2017-09-28 Janet Arras Straßenfahrbahnmarkierung mit großer Performance und Verfahren zur Anwendung
DE102017006843A1 (de) 2017-07-19 2019-01-24 Janet Arras Multifunktionale Straßenfahrbahnmarkierung mit großer Performanz und Verfahren zur Anwendung
DE102017006842A1 (de) 2017-07-19 2019-01-24 Janet Arras Ausstattungen zur Sicherheit im Straßenverkehr mit großer Performanz und Verfahren zur Anwendung
WO2019016274A1 (fr) 2017-07-19 2019-01-24 Arras Janet Substance luminescente à surface fonctionnalisée, composition et composition durcie la contenant et utilisation correspondante ainsi que procédé pour la fabrication d'un article marqué par luminescence

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1022621A (en) * 1963-02-15 1966-03-16 British Titan Products Producing pigments
US3410708A (en) 1964-08-05 1968-11-12 Du Pont Porous silica coated titanium dioxide pigment
FR1537805A (fr) * 1966-07-15 1968-08-30 Du Pont Pigments de bioxyde de titane traités par la silice et l'oxyde de zinc pour stratifiés de papier
US3591398A (en) 1968-04-05 1971-07-06 Du Pont Process for producing titanium dioxide pigments
US3599398A (en) 1970-01-12 1971-08-17 Ovitron Corp Method and apparatus for separating foreign matter from gases
GB1336292A (en) * 1970-01-15 1973-11-07 Laporte Industries Ltd Treatment of oxide pigments
US5886069A (en) * 1995-11-13 1999-03-23 E. I. Du Pont De Nemours And Company Titanium dioxide particles having substantially discrete inorganic particles dispersed on their surfaces
US5650002A (en) * 1995-11-13 1997-07-22 E. I. Du Pont De Nemours And Company TiO2 light scattering efficiency when incorporated in coatings
US6036999A (en) * 1997-07-03 2000-03-14 Zhao; Qian Qiu Method of preparing grinding media consisting essentially of sintered TiO2 particles
GB9822527D0 (en) * 1998-10-15 1998-12-09 Courtaulds Coatings Holdings Powder coating compositions
KR20070024627A (ko) * 2004-06-24 2007-03-02 이시하라 산교 가부시끼가이샤 이산화 티탄 안료 및 그 제조 방법 그리고 그것을 함유하는수지 조성물
DE102008026300A1 (de) * 2008-06-02 2009-12-03 Kronos International, Inc. Verfahren zur Oberflächenbeschichtung von anorganischen Festkörperpartikeln, insbesondere Titandioxid-Pigmentpartikel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013041217A1 *

Also Published As

Publication number Publication date
WO2013041217A9 (fr) 2015-03-19
US20130074734A1 (en) 2013-03-28
DE102011113896A1 (de) 2013-03-28
WO2013041217A1 (fr) 2013-03-28

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