AU2007224748A1

AU2007224748A1 - Titanium dioxide pigment coated with hollow bodies, and production method

Info

Publication number: AU2007224748A1
Application number: AU2007224748A
Authority: AU
Inventors: Siegfried Bluemel; Lydia Drews-Nicolai
Original assignee: Kronos International Inc
Current assignee: Kronos International Inc
Priority date: 2006-03-16
Filing date: 2007-03-08
Publication date: 2007-09-20
Anticipated expiration: 2027-03-08
Also published as: MY151114A; JP2009529613A; BRPI0708985A2; TW200740928A; KR20080102198A; AU2007224748B2; DE102006012564B4; SA07280100B1; WO2007104465A3; EP1994098A2; UA94075C2; RU2008140369A; JP5199894B2; CN101389714B; RU2443737C2; WO2007104465A2; CN101389714A; DE102006012564A1

Description

CERTIFICATE OF VERIFICATION I, Michaela Kunigkeit of Bergerhof 69, 42799 Leichlingen, Germany state that to the best of my knowledge the attached document is true and complete translation of International PCT Application No. PCT/EP2007/001997 Date Signature of translator Date Signature of translator TG 182WO 1 of 12 Titanium dioxide pigment coated with hollow bodies and production method Field of the Invention The invention relates to a titanium dioxide pigment of high opacity, a method for its manufacture and its use in decorative laminating papers or decorative foils. 10 Technoloqical Backqround of the Invention Decorative laminating papers and decorative foils are part of a decorative, thermosetting coating material, used with preference for finishing furniture surfaces, for laminate flooring and in interior finishing. Laminates is the term used to denote materials in which, for 15 example, several impregnated, stacked layers of paper, or paper and hardboard or fibreboard, are pressed together. The use of special synthetic resins achieves extraordinarily high resistance of the laminates to marring, impact, chemicals and heat. The use of decorative laminating papers (which is always also intended to mean decorative 20 foils below) makes it possible to produce decorative surfaces, where the decorative laminating paper serves not only as facing paper, e.g. to hide unattractive wood material surfaces, but also as a carrier for the synthetic resin. The demands imposed on decorative laminating paper include, among others, opacity (hiding power), light-fastness (greying resistance), colour-fastness, wet strength, suitability 25 for impregnation and printability. The economic efficiency of the manufacturing process for decorative laminating papers is determined by, among other things, the opacity of the pigment in the paper. In principle, a pigment based on titanium dioxide is eminently suitable for achieving the necessary opacity 30 of the decorative laminating paper. During paper manufacture, a titanium dioxide pigment, or a titanium dioxide pigment suspension, is usually mixed with a pulp suspension. In addition to pigment and pulp as the feedstock, use is generally also made of auxiliaries, such as wet strength agents, and further additives where appropriate. The interactions of the individual components (pulp, pigment, auxiliaries and additives, water) with each other contribute to 35 formation of the paper and determine the retention of the pigment. Retention is the capacity for retaining all inorganic substances in the paper during production.

TG 182 WO 2 of 12 It is known that an improvement in opacity can be achieved by special treatment of the surface of the titanium dioxide pigment. 5 US 5,942,281 A and US 5,665,466 A describe a surface treatment in which a first layer of aluminium oxide phosphate is applied at an acidic pH value of 4 to 6, and a second layer of aluminium oxide is precipitated in a pH range from 3 to 10, preferably at roughly pH 7. An improvement in retention is achieved by a third layer consisting of magnesium oxide, the result being that the pigment produced is characterised by consecutive layers of aluminium 10 oxide phosphate, aluminium oxide and magnesium oxide. US 6,962,622 B2 discloses a titanium dioxide pigment blend that is composed of a pigment with high greying resistance (pigment Type A) and a pigment with a coating displaying an elevated SiO 2 and AI 2 0 3 content, precipitated in fluffy form (pigment Type B). US 6,143,064 A describes the coating of pigment particles with precipitated calcium 15 carbonate, where the size of the calcium carbonate particles is between 30 and 100 nm. The titanium dioxide coated with calcium carbonate achieves higher opacity in the paper. In this context, the calcium particles assume the function of spacers, such that the pigment particles display better distribution in the paper. The minimum distance between the pigment particles is said to correspond roughly to the size of the pigment particles. 20 US 5,886,069 A and US 5,650,002 A describe TiO 2 pigment particles displaying both a continuous inorganic coating and a coating of discrete inorganic particles with a diameter of 5 to 100 nm. The surface coating sequence can be selected at random, as can the form of the discrete particles. Production is performed by mixing a colloidal suspension of the discrete particles with a TiO 2 slurry. 25 US 2003 0024437 Al discloses a pigment blend with pigment particles onto whose surface spherical particles, such as calcium carbonate, silicon oxide, aluminium oxide, zirconium oxide or titanium oxide, have been precipitated in-situ. 30 Object and Summary of the Invention The object of the invention is to provide an alternative titanium dioxide pigment with good opacity and good retention for use in decorative laminating papers. The object of the invention is furthermore to provide a method for manufacturing a titanium dioxide pigment of 35 this kind.

TG 182WO 3 of 12 The object is solved by a titanium dioxide pigment that contains titanium dioxide particles and where a layer containing aluminium phosphate, aluminium oxide and hollow bodies is located on the particle surface. The object is furthermore solved by a method for manufacturing a coated titanium dioxide 5 pigment, comprising the steps a) Provision of an aqueous suspension of uncoated titanium dioxide particles, b) Addition of an aluminium component and a phosphorus component, c) Addition of hollow bodies, d) Setting of the pH value of the suspension to a value in the range between 4 and 9. 10 Further advantageous versions of the invention are described in the sub-claims. Description of the Invention 15 Here and below, the term "oxide" is to be taken to also mean the corresponding hydrous oxides or the hydrates. All data disclosed below regarding pH value, temperature, concentration in % by weight or % by volume, etc., are to be interpreted as including all values lying in the range of the respective measuring accuracy known to the person skilled in 20 the art. When used in the context of the present patent, the term "significant quantity" or "significant content" indicates the minimum quantity of a component, upwards of which the properties of the mixture are affected in the framework of the measuring accuracy. The titanium dioxide pigment according to the invention is characterised by the use of hollow 25 bodies. The hollow bodies ca include hollow spherical shapes or spheres including hollow microbodies or hollow microspheres. The invention includes the use of hollow bodies during post-treatment. The hollow bodies are attached to the particle surface and act as spacers between the individual pigment particles. The hollow bodies can be of an inorganic and organic nature. They preferably display a mean diameter of 5 to 1,000 nm. The hollow bodies 30 are characterised by the inclusion of air, where the inclusion of air may possibly not be present until after drying of the pigment. Organic hollow bodies are used as extenders in paints, for example. The hollow bodies act as spacers between the pigment particles and, as a result of their entrapped air, lead to 35 higher hiding power by exploiting the favourable difference between the refractive indices of the pigment and air ("Qualitatsverbesserung - RopaqueTM Opaque Polymer zur TG 182 WO 4 of 12 Qualitatsverbesserung von Lacken und Farben" ["Quality Improvement - RopaqueTM Opaque Polymer for Improving the Quality of Paints and Coatings"], Phinomen Farbe 2/98, 1/99). The publication "Hollow latex particles: synthesis and applications" (McDonald et al., Advances in Colloid and Interface Science 99 (2002) 181 - 213) provides a review of the 5 manufacture of organic hollow spheres. An exemplary description of the manufacture of inorganic hollow spheres is given in "Nanoengineering of Inorganic and Hybrid Hollow Spheres by Colloidal Templating" (Caruso et al., Science 1998, Vol. 282, p. 1111). The patent application WO 02/074431 Al discloses the manufacture of inorganic hollow bodies and their use in catalysis and in photonics. 10 In the method according to the invention, a layer of aluminium-phosphorus compounds in a blend with hollow bodies and with aluminium oxide if applicable is precipitated on the TiO 2 particle surface. The composition is dependent on the quantities of the aluminium and phosphorus components used. For simplicity, this layer is referred to as the aluminium oxide 15 phosphate/hollow sphere layer below. The post-treatment method on which the invention is based starts with an aqueous, and preferably wet-milled, TiO 2 suspension (Step a)). Where appropriate, wet-milling is performed in the presence of a dispersant. The TiO 2 comprises uncoated TiO 2 particles, i.e. TiO 2 base 20 material particles, produced by the sulphate process (SP) or the chloride process (CP). The base material is usually stabilised, by addition of aluminium at a rate of 0.3 to 3% by weight, calculated as AI 2 0 3 , and with an oxygen surplus of 2 to 15% in the gas phase during oxidation of the titanium tetrachloride into titanium dioxide in the CP process, and by doping with AI, Sb, Nb or Zn, for example, in the SP process. 25 TiO 2 particles produced by the chloride process are used with preference. The method is performed at a temperature of under 80 'C, preferably at 55 OC to 65 OC. The suspension in Step a) can be set to be either alkaline or acidic, with a pH value of preferably > 9 or < 4. 30 In Step b), an aluminium and a phosphorus component are added. Suitable aluminium components for the surface treatment method according to the invention are alkaline or acid reacting, water-soluble salts, e.g. sodium aluminate, aluminium sulphate, aluminium nitrate, aluminium chloride, aluminium acetate, etc. This selection is not to be interpreted as a restriction. The aluminium component is to be added in a quantity of 1.0 to 5.0% by weight, 35 preferably 1.5 to 4.5% by weight, particularly 2.0% by weight, calculated as AI 2 0 3 and referred to the TiO 2 particle.

TG 182WO 5 of 12 Suitable phosphorus components are inorganic compounds, such as alkali phosphates, ammonium phosphate, polyphosphates, phosphoric acid, etc. This selection is not to be interpreted as a restriction. Particularly suitable are disodium hydrogenphosphate or phosphoric acid. The phosphorus component is added in a concentration of 1.0 to 5.0% by 5 weight, preferably 1.5 to 4.0% by weight, particularly 2.0 to 3.0% by weight, calculated as

P

2 0 5 and referred to the TiO 2 particle. The AI and the P component can be added to the suspension in any order, individually one after the other, or simultaneously. 10 A subsequent Step c) involves the addition of organic or inorganic hollow bodies with a mean diameter of 5 to 1,000 nm, preferably of 400 to 600 nm. The product Ropaque T M from Rohm & Haas, for example, is open to consideration for use as organic hollow spheres. Ropaque T M consists of styrene/acrylic copolymer beads. Other latex or polymer hollow spheres are also suitable. However, this list is not to be interpreted as a 15 restriction of the invention. Rather, all organic hollow spheres that display the required particle diameter in the range from 5 to 1,000 nm and are stable at the pH values occurring are in principle open to consideration. The inorganic hollow spheres described in the prior art include both glass hollow spheres and ceramic hollow spheres in general, and also TiO 2 hollow spheres in particular. It is again 20 the case here that all kinds of inorganic hollow bodies can in principle be used in the framework of the invention, provided that they display the required mean particle diameter of 5 to 1,000 nm and provided that they are stable at the pH values occurring. The person skilled in the art will select the appropriate hollow bodies on the basis of framework conditions, such as processibility, cost, etc. 25 The hollow bodies are added in a quantity of 1 to 15% by weight, referred to the uncoated TiO 2 particles. In a further subsequent Step d), the pH value of the suspension is set to a value in the range from 4 to 9 by adding a pH-regulating component. The pH-regulating component used can 30 be an acid or a lye. Examples of the acid that can be used are sulphuric acid, hydrochloric acid, phosphoric acid or another suitable acid. Moreover, a corresponding acid-reacting salt, such as aluminium sulphate, can also be used in place of the acid. It is furthermore possible to use an acidic metal salt solution, e.g. of cerium, titanium or zirconium, such that precipitation takes place jointly with the aluminium oxide phosphate/hollow sphere layer. 35 Sodium hydroxide solution is preferably used as the lye. Alkaline-reacting salts are also TG 182 WO 6 of 12 suitable. The person skilled in the art is familiar with suitable pH-regulating compounds. The selection is thus not to be interpreted as a restriction of the invention. It has proven advantageous to apply, in a subsequent Step e), a layer of aluminium oxide to 5 the aluminium oxide phosphate/hollow sphere layer in such a way that the pH value is maintained in the range from 4 to 9 e.g. by parallel addition of an alkaline and an acidic aluminium component (e.g. sodium aluminate / aluminium sulphate), or by addition of an alkaline aluminium component, such as sodium aluminate, and an acid, e.g. sulphuric acid or hydrochloric acid, or by addition of an acidic aluminium component, such as aluminium 10 sulphate, together with a lye, e.g. NaOH. In this context, either the components can be added in such a way that the pH value remains constant at a value in the range from 4 to 9, or the components can be added in such a combination that the pH value varies within the pH value range from 4 to 9 during addition. The person skilled in the art is familiar with these procedures. Suitable for setting the pH value are, for example, lyes or acids (e.g. NaOH / 15 H 2

SO

4 ), or alkaline or acid-reacting salt solutions (e.g. sodium aluminate / aluminium sulphate). It has proven particularly advantageous to perform treatment at the pH value previously set in Step d). As and when required, the pH value is subsequently set to between 5 and 8 in a Step f), e.g. 20 using lyes / acids (e.g. NaOH / H 2

SO

4 or HCI) or using alkaline / acidic salt solutions, such as sodium aluminate / aluminium sulphate. The quantity of the aluminium compounds used in Steps d), e) and f), calculated as A1 2 0 3 , is to be added to the quantity of A1 2 0 3 already used in Step b). The sum total of the aluminium 25 compounds used in Steps b) to f), calculated as A1 2 0 3 and referred to the uncoated TiO 2 particle, is ideally 1.0 to 9.0% by weight, preferably 3.5 to 7.5% by weight, particularly 5.5% by weight. Similarly, the quantity of the phosphorus component possibly used in Steps d) and e), calculated as P 2 0 5 , is to be added to the quantity of P 2 0 5 s used in Step b). The sum total of the phosphorus compounds used in Steps b) to e), calculated as P 2 0 5 , is thus ideally 1.0 30 to 5.0% by weight, preferably 1.5 to 3.5% by weight, and particularly 2.0 to 3.0% by weight, calculated as P 2 0 5 and referred to the uncoated TiO 2 particle. Together with the AI and the P component, other metal salt solutions, e.g. of Ce, Ti, Si, Zr or Zn, can be added to the suspension in Step b), subsequently being precipitated jointly onto 35 the particle surface in Step d) as a phosphate or oxide in the aluminium oxide phosphate/ hollow sphere layer.

TG 182 WO 7 of 12 It is furthermore possible, either before Step e) or after Step e), to apply a further inorganic layer as known from the prior art (e.g. compounds containing Zn, Ti, Si). In a preferred embodiment of the method according to the invention, the starting point is an 5 alkaline TiO 2 suspension. To this end, Step a) first involves setting the suspension to a pH value of at least 10 using suitable alkaline compounds, e.g. NaOH. If wet-milling is performed, this should ideally be done before the milling operation. In Step b), an aluminium and a phosphorus component are then added to the suspension, each in the form of an aqueous solution. During addition of the components, the pH of the 10 suspension is maintained at a value of at least 10, preferably at least 10.5, and particularly preferably at least 11. Sodium aluminate is particularly suitable as the alkaline aluminium component. If an acid reacting compound is used, such as aluminium sulphate, the addition of which would reduce the pH value to below 10, it has proven advantageous to compensate for this effect by 15 adding a suitable alkaline compound, such as NaOH. The person skilled in the art is familiar with suitable alkaline compounds and the quantities required for maintaining the pH at a value of at least 10. In the case of phosphorus components whose addition would reduce the pH value to below 10, it has likewise proven advantageous to compensate for this effect by adding a suitable 20 alkaline compound, such as NaOH. The person skilled in the art is familiar with suitable alkaline compounds and the quantities required for maintaining the pH at a value of at least 10. The Al and the P component can be added to the suspension in any order, individually one after the other, or simultaneously. 25 In the subsequent Step c), the organic or inorganic hollow bodies with a mean diameter of 5 to 1,000 nm, preferably 400 to 600 nm, are added, in which context the pH value of the suspension does not drop below 10, preferably not below 10.5, particularly not below 11. In the subsequent Step d), the pH-regulating component is added, such that a pH value in the range from 4 to 9 is obtained. 30 In an alternative embodiment of the method according to the invention, the surface treatment according to the invention is started in the acidic pH range. In this case, Step b) involves the addition of such aluminium and phosphorus components that the pH value of the suspension is subsequently below 4. The person skilled in the art is 35 at liberty to already reduce the pH value in Step a) by means of a suitable acid, or to reduce the pH value to below 4 in Step b) using a suitable combination of the components, adding TG 182 WO 8 of 12 an acid where appropriate. For example, the combination phosphoric acid / sodium aluminate or disodium hydrogenphosphate I aluminium sulphate is suitable. The components can be added to the suspension in any order, individually one after the other, or simultaneously. 5 In Step c), only hollow bodies are used that are stable at an acidic pH value. In Step d), a pH-regulating component is again added, as a result of which a pH value in the range from 4 to 9 is obtained. The surface-treated TiO 2 pigment is separated from the suspension by filtration methods 10 known to the person skilled in the art, and the resultant filter cake is washed in order to remove the soluble salts. To improve the light-fastness of the pigment in the laminate, a nitrate-containing compound, e.g. KNO 3 , NaNO 3 , AI(NO3) 3 , can be added to the washed filter paste in a quantity of 0.05 to 0.5% by weight, calculated as NO 3 , before or during subsequent drying. During subsequent milling, e.g. in a steam mill, an organic compound can be added 15 to the pigment, taken from the range customarily used in the manufacture of TiO 2 pigments and familiar to the person skilled in the art, such as polyalcohols (trimethylolpropane). As an alternative to addition of the nitrate-containing compounds before or during drying, such substances can also be added during milling. 20 Compared to the reference pigment, the pigment manufactured according to this method displays improved opacity and is optimally suited to use in decorative laminating paper or decorative coating materials, respectively. The surface treatment method according to the invention is customarily performed in batch 25 mode. It is, however, also possible to perform treatment continuously, in which case suitable mixing equipment, such as is familiar to the person skilled in the art, must guarantee sufficiently thorough mixing. 30 Examples An example of the invention is described below, yet the example is not intented to restrict the scope of the invention. 35 Example: TG 182 WO 9 of 12 A sand-milled TiO 2 suspension from the chloride process with a TiO 2 concentration of 350 g/I was set to a pH value of 10 with NaOH at 60 OC. While stirring, 2.0% by weight A1 2 0 3 were added to the suspension in the form of sodium aluminate solution. After stirring for 15 minutes, 2.4% by weight P 2 0 5 were added in the form of disodium hydrogenphosphate 5 solution. This was followed by stirring for a further 15 minutes. Next, 30% Ropaque Ultra Emulsion (polymer hollow beads, Rohm & Haas), corresponding to a styrene/acrylic copolymer active substance content of 2% by weight referred to TiO 2 , was added and stirred for a further 15 minutes. In the next step, the suspension was set to a pH value of 5 by adding aluminium sulphate solution corresponding to 2.6% by weight A1 2 0 3 . Subsequently, 10 0.7% by weight A1 2 0 3 was added in the form of parallel addition of sodium aluminate and aluminium sulphate solution, such that the pH value was maintained at 5. After stirring for 30 minutes, the suspension was set to a pH value of approx. 5.8 with the help of an alkaline sodium aluminate solution, filtered and freed of the water-soluble salts by washing. The washed filter paste was dried in a spray drier, adding 0.25% by weight NO 3 in 15 the form of NaNO 3 , and subsequently steam-milled. A transmission electron micrograph of the example pigment shows the hollow spheres attached to the pigment surface in Figures la and lb. Reference example: 20 A sand-milled TiO 2 suspension from the chloride process with a TiO 2 concentration of 350 g/l was set to a pH value of 10 with NaOH at 60 'C. While stirring, 2.0% by weight A1 2 0 3 were added to the suspension in the form of sodium aluminate solution. After stirring for 15 minutes, 2.4% by weight P 2 0 5 were added in the form of disodium hydrogenphosphate solution. Stirring for a further 15 minutes then followed. In the next step, the suspension was 25 set to a pH value of 5 by adding aluminium sulphate solution, corresponding to 2.6% by weight AI 2 0 3 . Subsequently, 0.8% by weight AI 2 0 3 was added in the form of parallel addition of sodium aluminate and aluminium sulphate solution, such that the pH value was maintained at 5. After stirring for 30 minutes, the suspension was set to a pH value of approx. 5.8 with the 30 help of an alkaline sodium aluminate solution, filtered and freed of the water-soluble salts by washing. The washed filter paste was dried in a spray drier, adding 0.25% by weight NO 3 in the form of NaNO 3 , and subsequently steam-milled.

TG 182WO 10 ot 12 Test Methods and Test Results Test Methods 5 For assessing the optical properties of the decorative laminating papers, and thus the quality of the titanium dioxide pigment, it is important to compare decorative laminating papers with an identical ash content. Sheets of decorative laminating paper with a sheet weight of roughly 80 g/m 2 and an ash content of roughly 30 g/m 2 were produced. The person skilled in the art is familiar with the procedure and the auxiliaries used. 10 The titanium dioxide content (ash) of a sheet and the pigment retention were subsequently determined. a) Ash content The titanium dioxide content was determined by incinerating a defined weight of the 15 produced paper in a rapid incinerator at 900 oC. The TiO 2 content by mass (ash) in % by weight was obtained by weighing the residue. The following formula was used as the basis for calculating the ash content: Ash content [g/m 2 ] = (Ash [% by weight] x Grammage [g/m 2 ]) / 100 [%]. 20 b) Retention The retention is defined as the capacity to retain all inorganic substances in the sheet of paper on the wire of the paper machine. The "one-pass retention" determined here indicates the percentage retained during a single pass through the paper machine. The ash content in percent, referred to the content by mass of the pigment used relative to the total solids in the 25 suspension, yields the retention: Retention [%] = Ash [%] x (Pigment weight [q] + Pulp weight [ql) Pigment weight [g] b) Optical properties 30 The optical properties of the pigments were determined in laminates. To this end, the decorative laminating paper was impregnated with a modified melamine impregnating resin and pressed into laminates. The sheet to be impregnated with resin was completely immersed in the melamine resin solution, subsequently drawn between two doctor blades to ensure application of a specific amount of resin and then immediately pre 35 condensed at 130 'C in a recirculating-air drying oven. The amount of resin applied was 120 to 140% of the weight of the sheet. The sheet had a residual moisture content of approx. 6% TG 182WO 11 of 12 by weight. The condensed sheets were combined into books with phenolic resin-impregnated core papers and white/black underlay paper. The laminate structure used for assessing the test pigments comprised 11 layers: decorative laminating paper, white/black underlay, core paper, core paper, core paper, white underlay, 5 core paper, core paper, core paper, white/black underlay, decorative laminating paper. The books were pressed for 300 seconds with the help of a Wickert Type 2742 laminating press at a temperature of 140 'C and a pressure of 900 N/cm 2 . The optical properties of the laminates were measured using a commercially available spectrophotometer. 10 In order to assess the optical properties of the laminates, the optical values of the decorative laminating papers (CIELAB L*, a*, b*) to DIN 6174 were determined with the help of the ELREPHO® 3000 colorimeter over white and black underlay. The opacity is a measure of the light transmission of the paper. The following parameters were selected as a measure of the opacity of the laminates: CIELAB L*black, the brightness of the laminates measured over black 15 underlay paper, and the opacity value L [%] = Yblack/Ywhite X 100, determined from the Y-value of the decorative laminating papers measured over black underlay paper (Yblack) and the Y value measured over white underlay paper (Ywhite). Test Results 20 The Table shows the test results for laminates produced using the pigment according to the invention (Example) and a reference pigment (Reference example). Compared to the reference pigment, the pigment according to the invention demonstrates improved opacity. 25 TABLE Pigment Opacity Retention L*black L [%] [%] 30 Example 90.3 91.1 69 Reference example 90.1 90.7 71 35

Claims

1. Titanium dioxide pigment comprising titanium dioxide particles, whereby a coating is located on the particle surface containing aluminium phosphate, aluminium oxide and hollow bodies.

2. Titanium dioxide pigment according to claim 1 characterized in that the hollow bodies display an average diameter of 5 to 1,000 nm.

3. Titanium dioxide pigment according to claim 1 or 2 characterized in that the aluminium content of the coating is 1.0 to 9.0 % by weight, preferably 3.5 to 7.5, in particular 5.5 % by weight calculated as A1 2 0 3 .

4. Titanium dioxide pigment according to one or more of claims 1 to 3 characterized in that the phosphorus content of the coating is 1.0 to 5.0 % by weight, preferably 1.5 to 3.5 % by weight, in particular 2.0 to 3.0 % by weight calculated as P 2 0 5 s.

5. Method for manufacturing coated titanium dioxide pigment particles comprising the steps a) providing an aqueous suspension of uncoated titanium dioxide particles, b) adding an aluminium and a phosphorus component, c) adding a component comprising hollow bodies, d) setting the pH value of the suspension to a value in the range of roughly 4 to 9.

6. Method according to claim 5 characterized in that in step a) the pH value of the suspension is at least 10 and in step b) the pH value of the suspension is kept at a value of at least 10.

7. Method according to claim 5 characterized in that in step b) the pH value of the suspension turns to below 4.

8. Method according to one of claims 5, 6 or 7 characterized in that the hollow bodies display an average diameter of 5 to 1,000 nm. TG 182 WO 2 von 3

9. Method according to one or more of claims 5 to 8 characterized in that in a step e) at a pH value of roughly 4 to 9 a further aluminium coating is applied.

10. Method according to one or more of claims 5 to 9 characterized in that the sum total of the aluminium compounds added is 1.0 to 9.0 % by weight, preferably 3.5 to 7.5 % weight and in particular 5.5 % by weight calculated as A1 2 0 3 .

11. Method according to one or more of claims 5 to 9 characterized in that the sum total of the phosphorus compounds is 1.0 to 5.0 % by weight, preferably 1.5 to 3.5 % weight and in particular 2.0 to 3.0 % by weight calculated as P 2 0 5 s.

12. Method according to one or more of claims 5 to 11 characterized in that in step b) further metal salt solutions of e.g. Ce, Ti, Si, Zr or Zn are added to the suspension together with the Al- and the P-component.

13. Method according to claim 11 characterized in that in a step f) the final pH value of the suspension is set to roughly 5 to 8.

14. Method according to one or more of claims 5 to 13 characterized in that in step d) an acid metal salt solution of Ce, Ti or Zr is used to control the pH value.

15. Method according to one or more of claims 5 to 14 characterized in that in a subsequent step the pigment particles are treated with nitrate, so that the finished pigment contains up to 1.0 % by weight nitrate.

16. Method according to one or more of claims 5 to 15 characterized in that in a subsequent step the pigment particles are milled together with an organic substance.

17. Method for manufacturing coated titanium dioxide pigment particles comprising the steps a) providing an aqueous suspension of uncoated titanium dioxide particles, whereby the pH value of the suspension is at least 10, b) adding an aluminium and a phosphorus component, whereby the pH value of the suspension is kept at a value of at least 10, c) adding a component comprising hollow bodies, d) setting the pH value of the suspension to a value in the range of roughly 4 to 9, TG 182 WO 3 von 3 e) applying a layer of aluminium oxide at a pH value of roughly 4 to 9.

18. Titanium dioxide pigment particles manufactured according to one or more of claims 5 to 17.

19. Use of titanium dioxide pigment according to one or more of claims 1, 2, 3, 4,18 when manufacturing decorative laminating paper.

20. Decorative laminating paper containing the titanium dioxide pigment according to one or more of claims 1, 2, 3, 4,18.

21. Use of decorative laminating paper containing titanium dioxide pigment according to one or more of claims 1,2, 3, 4,18 when manufacturing decorative coating materials.

22. Decorative coating material containing decorative laminating paper according to claim 20.