DE2249678A1 - FLOWABLE SUSPENSIONS CONTAINING TITANIUM PIGMENTS OR TITANIUM FILLERS WITH A HIGH SOLID CONTENT - Google Patents

Description

Bayer Aktiengesellschaft

Central Department Patents, Trademarks and Licenses ■

Gr-her 5Ö & Leverkusen, Bayerwerk

Flowable ones containing titanium pigments or titanium fillers High solids slurries

The invention relates to slurries of stabilized titanium pigments or titanium fillers with high solids contents and a process for their production. The slurries are obtained by dispersing the pigments in water in the presence of basic aluminum salts. A preferred application of the method according to the invention is for anatase and rutile. .

Highly concentrated aqueous suspensions ("slurries") of TiOp pigments are becoming increasingly important. "Highly concentrated" is generally understood to mean a solids content above about 50% by weight, based on the weight of the suspension. Such slurries have a number of handling advantages over powdered pigments. Because of their physical state, they can be conveniently transported in tanks instead of on pallets. »Their pumpability also enables faster and more efficient transport than solids. Another and very considerable advantage is that no dispersing plant is required for incorporation into the pigmenting system. and the pigment suspensions more accurate and more convenient (no sacks Transport and dusting of the pig-

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ment powder) as the corresponding pigment powder. In order to make the most of these advantages To ensure the lowest possible cost, the aqueous pigment suspensions must have a high solids content have a viscosity that is as low and stable as possible and must not tend to settle. Also must be a good one Compatibility with the system to be pigmented to be guaranteed.

Attempts have been made for some time to produce high-percentage TiOp and especially anatase suspensions, which are of particular importance for the paper industry. For example, German Offenlegungsschrift 1 810 042 describes a process for producing stable 60-80 # anatase suspensions which contain an alkanolamine as a dispersant and a polysaccharide to prevent sedimentation. German Offenlegungsschrift 2 044-510 mentions high-percentage anatase slurries which are stabilized with a mixture of alkanolamine and sodium hexametaphosphate. According to another method (German Offenlegungsschrift 2 045 141), a stable viscosity of TiO ₂ and especially anatase slurries of high solids is achieved by adding a mixture of non-volatile polyhydric alcohols such as sorbitol with alkanolamines such as triethanolamine. According to a method described in German Offenlegungsschrift 1 542 202, aqueous inorganic solid suspensions can also be stabilized by a mixture of alkali silicates with alkali salts of aminopolyphosphonic acids.

Most of the processes mentioned have the disadvantage that they can predominantly only be used for anatase. Since the mentioned Dispersions contain an alkanolamine, they have

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has a weakly alkaline pH value (generally between pH 8 and pH 10).

As a result of its crystal and surface structure, which is different from anatase if the behavior of aqueous rutile suspensions differs considerably from that of anatase in general, see above that the dispersing and stabilizing substances that can be used for anatase are only partially or not transferred to rutile can be. In addition, rutile pigments have more or less large amounts of aftertreatment substances contained on the surface, e.g. AIpO.,. aq, SiOg.aq. or Aluminum silicates, so that there are no more free TiOp surfaces present what results in changed surface properties expresses. Usually used dispersants therefore often show no or only weak effects.

However, it is of considerable technical interest to also produce aqueous, high-percentage suspensions of aftertreated rutile pigments. Such slurries are important, for example, for the disperse paint sector and for spray-drying processes which are to be carried out _{following an aftertreatment of a TiO 2 pigment.} For economic reasons, suspensions that are as low in water as possible, but capable of flowing, must be present for this process.

The present invention relates to flowable, aqueous suspensions of titanium or titanium pigments fillers with a solids content of about 50 to 80 wt -.% _T characterized in that the titanium-containing suspensions contain basic aluminum salts. Furthermore, the present invention relates to a method for producing flowable,

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aqueous suspensions of titanium pigments or titanium fillers with a solids content of about 50 to 80 Gew .- #, which is characterized in that the Basic aluminum salts are added to titanium pigments or titanium fillers before, during or after suspension in an aqueous medium.

The present invention is advantageously suitable for titanium pigments and titanium fillers, although this designation preferably includes rutile or anatase, but is also intended to include other titanium compounds such as titanium phosphates, alkali poly titanates, alkaline earth titanates, and titanates of polyvalent metals or mixtures thereof. Examples are: K ₂ Ti ₄ O ₉ , K ₂ Ti ₆ O ₁₃ , Na ₂ Ti ₆ O ₁₃ , Na ₂ Ti ₅ O ₁₁ , K ₂ Ti ₅ O ₁₁ ,

7y \ TPiüi ndPT ¹ 7n Ti On

According to the invention, our basic aluminum salts are to be understood as meaning the following types of compounds:

a) Aluminum salts of predominantly weak organic acids with pK values above 1, such as aluminum

tartrate, aluminum citrate, aluminum benzoate, aluminum rhodanide, Aluminum oxalatoformate, aluminum salcylate and the Al salt of amidosulfonic acid, the compounds preferably being used which are described in the solution is predominantly in the form of aluminum chelate compounds;

b) compounds with the general formula Alp / ~ "(- 0-R) ₂ = X_7 ,;

c) Compounds with the general formula Al / ^ O-R-Z__7-i

d) Compounds with the general formula Al / ~ (-0-R) ^ I

e) Compounds with the general formula

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where in the formulas, ■. ·

R for an alkylene radical with 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as methylene (-CH ₂ -), ethylene (-CHp-CH-), optionally also for a branched alkylene radical such as isopropyleni-CiCH- ^ g- ) or for an arylene radical (- ^ jh ~) - *

X for a simple or alkyl group-substituted one (1-4

Carbon atoms) imino group (-NH-);
Y for a sulfonic acid residue (-SO ^ -), a carboxylic acid residue

(-COO-) or a phosphonic acid residue (-HP0 -, -); Z stands for a simple or alkyl group-substituted (1-4 C atoms) amino group (-NHg-).

Examples of the formula type b) are the Al compound of the diethanolamine Alg / JÖCHgCHg) ₂ NH _- / for the formula type c) the Al compound of the monoethanolamine Al (OCHgCHg-NHg) ^, for the formula type d) the Al compound des Triethanolamine .Al (OCHgCHg) ^ N and for the formula type e) the Al compounds of gycin Al (NHgCHgCOO) ₃ , taurine (NH ₂ CHgCHgSO ₃ ) JU, sulfanilic acid AIi-O ₃ S - ^ - NHg) ₃ and the Al salt of bis (hydroxyethyl) methylaminomethylphosphonic acid. Al ^ O ₃ P-CH ₂ -N (CgH ₄ OH) g_7 ₃ . .

CH ₃

f) Furthermore, basic aluminum salts are within the meaning of the invention Al salts of inorganic acids with a ratio of Al cation to anion (without consideration of hydroxyl anions) with values from 0.5 to 5 *, preferably 1.0 up to 3.0. The term "basic" is not intended to include an alkaline reaction of these salts, but only to express the fact that in these salts formally stoichiometric consideration predominantly OH anions exist, i.e. only a small part of the OH anions of Al (OH) are replaced by acid anions. Of- such to-

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The latter aluminum salts are particularly suitable salts with monovalent anions. Examples of such salts ~ are, for example, the compounds Al (OH) ₂ Cl (ratio Al to Cl = 1: 1), Al ₂ (OH) ₅ Cl (ratio Al to Cl = 1: 0.5), Al (OH) _{2 5} (N0,) ₀ ^ (ratio of Al to NO, = 1! 0.5) etc.

The production of this last-mentioned type of basic salts can be carried out in any way according to the known production processes for basic aluminum salt solutions, as for example in Gmelins Handbuch der Inorganischen Chemie, 8th Edition, No. 35 * Aluminum Part B, page 117 to 125, page 155 ff. and page 205 f (1934) are described. Then basic aluminum salts for example through incomplete precipitation of aluminum salts by alkaline or H-ions consuming Precipitation reagents, through complete precipitation of aluminum salts and subsequent peptization of the isolated alumina aquat with acids or hydrolytically split metal salts, by hydrolysis of aluminum salts or directly through Activated aluminum can be peptized with water, hydrolytically cleaved folds or acids.

The above types of basic aluminum salts (a-f) The pigment or filler suspensions to be "liquefied" can either be in crystalline form or as aqueous Solutions are added. The amounts to be used depend primarily on the type of pigments or Fillers from which are to be liquefied.

Amounts between 0.05 to 3 % by weight of Al ₂ O (as Al ₃ O., calculated and based on the titanium compound) in the form of the basic aluminum salts, preferably amounts between 0.1 to 0.9% by weight, have proven practical. # Al ₂ ⁰ V ^{In the sense of the} invention, titanium pigments or powder

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substances without pre-stabilization and post-treatment as well as titanium compounds which have been subjected to pre-stabilization, for example with ZnO or AlpCu and / or an inorganic and / or organic post-treatment in a known manner. For example, inorganic aftertreatments with SiO _p , AlpO - ,,. TiOp, ZrOp, SnOp _-9 MgO ₃ ZnO and / or phosphates or organic aftertreatment with amines, hydroxyalkanes, epoxides, etc. can be used upstream.

In the preparation of the high-percentage suspensions, the procedure is advantageously such that the pigment or filler is mashed in the required amount of water in stages with the aid of a high-speed and high turbulence-generating stirrer (dissolver, mixing siren, turbine stirrer, propeller stirrer, etc.) and when thickened the substances according to the invention for "liquefaction! ¹ " are gradually added until the desired percentages in terms of pesticide content and content of "liquefying agent" are reached solid substances according to the invention are "liquefied".

The suspensions "liquefied" according to the invention can be dried and be married. The pigments or fillers obtained can be reused in one operation with water "liquefied" to form high-percentage suspensions.

In an analogous manner, it is possible to use dry pigment or filler powder with the "liquefaction" according to the invention

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basic aluminum salts used in the solid state to, mix or grind and then the mixture obtained To be mixed with water in one operation to form a high-percentage suspension.

The suspensions prepared according to the invention can, without that their properties deteriorate, with smaller ones Amounts of additives are provided, which are subsequently used as stabilizers are designated. For example, known fillers such as barium sulfate, Calcium carbonate, dolomite, silicates or mica in amounts of 0.03 to 5% by weight (based on the titanium compound) and / or known thickeners such as cellulose ethers, preferably carboxymethyl cellulose and / or hydroxyethyl cellulose, Polyethylene glycol and polyethylene oxide and wetting agents such as alkyl, aryl or alkyl aryl sulfonates are added to the suspensions can be added to expand the scope.

The suspensions prepared by adding the stabilizers mentioned can - if z. B. a longer storage is provided - produce in a stable form for several weeks. The low tendency of the suspensions obtained according to the invention to form sediment, to sediment or to change the viscosity is a particularly valuable property here. Measuring the efflux time is used in a standard measuring cup according to DIN 53 211 for checking the viscosity with a nozzle diameter of 4 mm (flow time for H ₂ O at 20 ⁰ C 10 - 11 seconds).

The solid polyethylene glycols or polyethylene oxides which can be used as stabilizers can have molecular weights from 4000 to over 10 ⁶ . The higher molecular types are preferred when a slightly more viscous consistency is required, lower molecular types for low-viscosity suspensions

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sions. The polyethylene oxides are used in amounts of 0.05 wt .-% (based on titanium compound) to 1 wt -.% Effective, preferably carried out with quantities of 0.1 to 0.5%. The organic sulfonates which have the same stabilizing effect and which also already have effectiveness in the iron range from 0.05 to 1% by weight, preferably from 0.1 to 0/5% by weight (based on titanium compound), are involved they are connections ^. which are either esters or salts of sulfonic acids, such as, for example, lauryl sulfate, fatty alcohol sulfonate, dinaphthyl methanesulfonate, dibutyl naphthalene sulfonate or lignin sulfonate. Dinaphthyl methane sulfonate and dibutyl naphthalene sulfonate are preferably used. By adding known fillers and / or thickeners as stabilizers to the suspensions liquefied according to the invention, the formation of sediments can be avoided even after prolonged storage times. Among the fillers, preference is given to using silicates, for example pyrophyllite, ffiontmorillonite, mica in amounts between 0.03 and 5% by weight, preferably between 0.1 and 1% by weight (based on titanium pigment). As a thickening agent, between 0.03 and 0.07 parts by weight (based on the titanium compound) are preferably added to the suspensions.

The stabilized suspensions obtained in this way can through conventional drying processes into solid pigment or powder powder are transferred, which form the stabilized suspensions described when slurried with water. The dry pigments and fillers provided with basic aluminum salts and stabilizers are in this form can be stored at any time ”.

The following examples are intended to explain the invention in more detail:

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example 1

70.6 kg TiO ₂ in the form of a technical TiOp hydrolyzate with a content of 8 # HpSO. were mixed with a solution of 24.4 kg KpCO ,, 5.0 kg KpSO and 2.57 kg KP and a solution of 5.54 kg Al (NO,),. 9 HpO was added dropwise in water. The reaction mixture was evaporated to dryness in a paddle dryer, and a mass was obtained which, based on the dry substance, was 68.4 # TiO ₂ , 15.9 $> K ₂ CO ₅ , 14.5 # K ₂ SO ₄ as a mineralizer and 1.20 # AIP, as a modifier. The mixture was heated in 150 min. To 900 ⁰ C and to a fibrous white pigment of the composition .. KpTigO reacted whose pigment particles micron in diameter from 0.2 to 0.5 micron and a length in the range 3 to 15 having .

The Pigmen + was slurried in water, the pigment needle agglomerates were broken up by briefly stirring with a mixer siren, and the pigment cake was filtered off, washed and sucked dry. The filter cake, which made a firm impression, contained only 34.136 pesticides because of the needle shape of the pigment particles. By filtering off the filter cake in a filter press, a solids content of $ 46.4 could be achieved. This filter cake was dry to the touch and could be crumbled. 13 g of solid basic aluminum chloride of the composition Al ₂ (OH) cCl · 3 HgO were then added to 2.81 kg of this filter cake, whereupon it began to dissolve. The pigment suspension obtained (46 % solids, 0.45 % Al ₂ O, based on solids) could now be homogenized by stirring and had a flow time from a DIN beaker with a 4 mm nozzle of 43 seconds (water value 10-11 Sec.). In this liquid form, the pigment suspension could be added to the paper roll and used for pigmenting paper.

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■ ■. 224 367 8 M.

be set »

In the same way could a suspension with 51 <fi solids and 0.68 # AIoO be produced (in the form of Al ₉ (QH) t-Cl), which had a more paste-like consistency, but was processed in the same way.

Example 2 ,

79.9 kg of TiO ₂ in the form of a technical TiOg hydrolyzate washed free of sulfuric acid with NH.OH were mixed with 162.8 kg of ZnO (molar ratio TiO ₂ : ZnO = 1: 2). An aqueous solution of 0.55 kg K ₂ GO ₅ and 0.13 kg Η, ΡΟ ^ .86.7 #ig (as setting chemicals) were added dropwise with stirring. The mixture was dried in a thin layer, mixed again and in 2 h Annealed at 850 ^° C. in a rotary kiln. A white pigment was obtained which, by X-ray analysis, showed _{the reflections of the compound.Zn 2} Ti _{5 Og.} ■

The product was subjected to wet grinding in a ball mill and the pigment suspension obtained was filtered off and washed. After vacuuming dry, the filter cake contained 58 io solids. By applying pressure, the filter cake could be further dewatered to a solids content of $ 67>. At this stage the filter cake appeared dry and could be cut with a knife. 1 kg of solid Al ₂ (OH) ₅ Cl. 3 H ₂ O was added., There was a liquefaction was obtained based obtain a pigment suspension having a solids content of 66.5 $> with a algo-z-content of 0.52 $ to solid. .

The pigment suspension showed an outflow time of 2 min same DIN cup as in example 1. It was a spray

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dryer and dried at? QO ° C Obtain pigment powder. ,

The dried pigment powder was mixed with an containing the formation of a $ 67> solids suspension necessary faasermenge added and stirred. Liquefaction occurred again. After dispersing with the dissolver, a suspension with the original properties was obtained.

Example 3

_{4055 g of a TiO 2} rutile pigment prepared by the sulfate process and calcined without stabilizing additives, but aftertreated _{with 1.0 3t TiOp and 3.0 # Al 2} O, were mixed with 1455 ml H ₂ O and 45.1 g of the basic aluminum salt Al ₂ (OH) ₅ Cl. 3 H ₂ O (corresponding to 0.5 $ Al ₃ O ₅ , based on) slurried to form a flowable suspension.

The suspension was produced in a 5 liter plastic container with the help of a 3-blade propeller stirrer (Propeller radius 30 mmf 1500 revolutions / minute).

For this purpose, 1455 ml of H ₂ O were placed in the plastic vessel. _{The TiO 2} pigment was then added in portions with stirring until the suspension had a TlOp content of 55% by weight and thickened. Approx. 10 g of Al ₂ (OH) ₅ Cl · 5 H ₂ O were then sprinkled into the viscous pigment paste, whereupon this liquefied again almost immediately and was completely circulated by the stirrer. _{TiO 2} pigment and the basic aluminum salt were then added alternately in portions _{until the pigment suspension had a TiO 2} content of 73% by weight (based on suspension weight). The suspension was stirred for a further 30 Hin.

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The density of the pigment suspension was 2.060, the outflow time in the DIN beaker with a 4 mm nozzle was 15 seconds. After a standstill The outflow time was measured again after 2 weeks and was now 12 seconds. After this time, on upper edge of the vessel, a 20 cm high wide neck bottle an approx. 1 cm high, cloudy, pigment-depleted layer formed, while at the bottom of the vessel an approx. 1.2 cm high, solid sediment was formed was to be found. The pH of the pigment suspension was 5.7. .

Example 4

Example 3 was repeated. After the 73% pigment suspension had been obtained, 12.2 g of polyethylene oxide (average molecular weight 1 to 3 million) were added in portions (stirring conditions as in Example 1) and the mixture was stirred for a further 15 minutes. The addition corresponds to 0.3 percent -. $> Polyethylene oxide based on TiO _2. The density of the pigment suspension was now 2.038. The outflow times in the DIN beaker following the preparation of the pigment suspension were 21 see. and determined after 2 weeks of standing for 20 seconds. After this standing time, neither a pigment-depleted layer nor a sediment had formed on the upper edge of the vessel.

Example 5

Example 3 was repeated. After the 73% pigment suspension had been obtained, 12.2 g of dinaphthyl methanesulfonate were added in portions (stirring conditions as in Example 1) and the mixture was stirred for a further 15 minutes. The addition corresponds to 0.3% by weight, based on TiO _2. The density of the pigment suspension was now 2.002. The outflow times in the DIN beaker following the preparation of the pigment suspension were 16.5 seconds

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and determined after 2 weeks of standing 14.5 seconds. After this The upper edge of the vessel neither had a lifetime of pigment Depleted layer, a sediment still formed at the bottom of the vessel.

Example 6

Example 3 was repeated with a TiO ₂ rutile pigment prepared by the sulfate process and calcined with a stabilizing addition of 1.2% by weight of ZnO (based on TiO _2). The pigment had additionally been aftertreated with 1.0 _{% by weight of TiO 2} >> 0.8% by weight of SiO ₂ and 2.2% by weight of Al ₂ O ₅ (all data based on TiO ₂ ). Instead of the basic aluminum salt Al ₂ (OH) ₁ -Cl described in Example 5. 3 H «0, 220 ml of an aqueous solution of the basic aluminum salt Al (OH) ₂ 5 (NO ₅ J _{0 5} (92.2 g Al ₂ O ₅ per liter) were used. This solution was obtained by dissolving aluminum powder in the calculated amount of dilute nitric acid.

_{1280 ml of H 2} O were placed in the stirring apparatus described in Example 3. The TiO ₂ pigment was then added in portions until the aqueous pigment suspension thickened at a solids content of about 40% (based on the weight of the suspension). By adding 100 ml of the basic aluminum nitrate solution, a thin-bodied pigment suspension could again be obtained. This was concentrated by the alternate addition of TiO ₂ pigment and further basic aluminum nitrate solution to a content of 73 parts by weight of TiO ₂ (based on the weight of the suspension). The suspension was stirred for a further 30 minutes to set constant conditions. A total of 220 ml of the basic aluminum salt _{solution and 4055 g of TiO 2} pigment were added.

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The density of the pigment suspension obtained was 2.12, the outflow time in the DIN beaker with a 4 mm nozzle was 15.5 seconds. The suspension had a pH value of 5 »5 * After a standing time The outflow time was measured again after 2 weeks and was now 12.5 seconds. After this time it had become on top Edge of the vessel (20 cm high wide-necked bottle) an approx. 0.7 cm strong, cloudy, pigment-depleted layer formed, while at the bottom of the vessel a thixotropic sediment approx. 1.5 cm high was to be found.

Example 7

Example 6 was repeated. Subsequently were poured 350 of the 73 wt .- # g aqueous pigment suspension to an enamelled sheet and then in a drying cabinet for 16 hours at 8O ^{p 0} O and 8 hours at 120 C-dried. The total weight of dried pigment powder was 260 g. The powder was then again mixed with 90 ml Η «0 and ground in a ball mill for 15 minutes. A low-viscosity pigment suspension was again obtained which had an outflow time of 14 seconds in the DIN beaker. exhibited.

Example 8

Example 6 was repeated. After the 73 # pigment suspension had been obtained, 12.2 g of polyethylene oxide (average molecular weight 1 to 3 million) were added in portions (stirring conditions as in Example 6) and the mixture was stirred for a further 15 minutes. The addition corresponds to 0.3 wt .- # polyethylene oxide, based on TiO ₂ . The outflow times in the DIN beaker were determined to be 26 seconds following the preparation of the pigment suspension and 34 seconds after a standing time of 2 weeks. After this standing time, there was neither a pigment-depleted layer on the upper edge of the vessel, nor on the base of the vessel

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Sediment formed.

The Pigmentsuspeneion was then poured onto a tray and dried in a thin layer at 60 ⁰ C. After drying, the cake obtained was crushed and stirred with water. The dried pigment was added in portions until the suspension was 73% TiO ₂ pigment. After about 30 minutes of homogenization, a pigment suspension was obtained which in terms of its properties matched the properties originally produced.

Example 9

To produce a high-percentage flowable suspension, a TiO ₂ -Hutil pigment prepared according to the sulfate process and calcined with a stabilizing addition of 0.5 (Jew.-Jt Al ₂ O, (based on TiO ₂ ) without subsequent treatment) was used.

The pigment suspension was produced in one

600 ml beaker with the propel described in Example 3 l stirrer at approx. 1000 revolutions / min.

_{143 ml of H 2} O were placed in the beaker. The T10 ₂ pigment was then added in portions until thickening occurred when the pigment suspension contained approx. 50% by weight TiO ₂ (based on the weight of the suspension). The pigment paste could be liquefied again by adding 2 g of the basic aluminum salt ₂ () ^ 3 H _{2 O.} In portions and alternately, the TiOg pigment and, when the pigment suspension was thickened, the basic aluminum salt was added until a pigment suspension with a solids content of 72.8% by weight (based on suspension weight) was obtained. A total of 4.48 g of de-basic

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Aluminum salt AIp (OH) ₁ -Cl. 3 HpO (corresponding to 0.5 Sew.-ji O ^, based on TiO ₂ ) and 400 g of TiOg pigment were added.

The pigment suspension showed rather an initial viscosity in DIlJ-Be (Expiry time) of 22 seconds.

Example 10

With the TiOp pigment described in Example 3, aluminum tartrate was used as the pigment paste to make it liquid an approx. 65 #ige suspension is produced.

In the apparatus described in Example 3, 1335 ml HgO submitted. After adding the TiO ^ pigment in portions the suspension thickened at a solids content of approx. 55 #

After adding 50 ml aluminum tartrate solution (85 g AIpO, per liter) the pigment suspension liquefied again. The TiOp pigment was added in portions and thickened in the case of thickening Aluminum tartrate (a total of 165 ml of the solution) was added to the suspension until the suspension had a solids content (a total of 2786 g TiÖp pigment) of 65% by weight. After the preparation, there was a flow-out time in the DIN beaker of 13 seconds, while 12 seconds were measured after 2 weeks. The density of the pigment suspension was 1.92.

Example 11

With an untreated anatase pigment (grinding in a Raymond mill) was made using aluminum aminotriethanolate an approx. 73 # aqueous pigment suspension produced as a pigment paste liquefier.

For this purpose, 1432 ml of HpO were placed in the apparatus described in Example 3. After adding the anatase in portions

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Pigment, the pigment suspension thickened with a pesticide content of approx. 55 wt .- # (based on suspension weight). After adding 10 g of aluminum aminotriethanolate, the pigment paste liquefied. - The aluminum compound was isopropylate aluminum by reacting with triethanolamine get "20.4 g of aluminum isopropoxide were mixed well with 14.9 g of triethanolamine and then heated in an oil bath at 16O ⁰ C. The reaction lasted about 2 hours (reflux condenser), the isopropanol formed was distilled off and the solid product was recovered at the end of the reaction.

After the pigment paste had liquefied, anatase pigment and the aluminum salt were alternately added until the TiOp suspension had a solids content of 73% by weight (based on the weight of the suspension). A total of 4055 g of anatase pigment and 34 g of aluminum aminotriethanolate (0.25 wt. 56 AlpO ,, based on TiO ₂ ) were added. The pigment suspension had a density of 2.15 and a pH of 8.8.

The outflow time from the DIN cup was after preparation 18 seconds and after a standing time of 3 1/2 weeks (0.4 cm thick, pigment-depleted layer, slightly more thixotropic Sediment) 19 see.

Example 12

Example 11 was repeated with the modification that the anatase pigment was thoroughly mixed on a roller block with a mica filler (1.0% by weight, based on TiOg) before being incorporated into the aqueous pigment suspension . The finished pigment suspension had an anatase content of 73% by weight. In addition to the filler, it contained 0.25 wt

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pO ^ ₅ (based on TiOp) as aluminum aminotriethanolate. After the preparation, the flow time from the DIN beaker was 25 seconds. After a standing time of 2 weeks, neither an upper surface layer depleted in pigment nor a sediment could be observed in the preparation vessel.

Example 13

Example 11 was repeated. After the pigment suspension had been prepared, a solution of 2 g of carboxymethyl cellulose (average molecular weight approx. 600) in 100 ml of water was stirred into the suspension with the aid of a turbine _{stirrer, which then had a TiO 2} content of 73% by weight (based on the suspension weight) ) exhibited. The outflow time from the DIN cup was 23 seconds after preparation and 24 seconds after standing for 2 weeks. After this time, neither a pigment-depleted upper edge layer nor a sediment could be observed in the production vessel. The 73% TiOg suspension contained 0.25% by weight (based on TiO ₂ ) AlgO-z as aluminum aminotriethanolate and 0.05. Wt -.% (Based on TiO ₂₎ carboxymethylcellulose.

Example 14

From 196 mX of a basic Al nitrate solution (dissolved as Al (OH) _{2 5} (NO ₅ ) _O ^), the 81.6 g Al ₂ O, /! contained, by adding 12.6 g of aqueous ammonia solution (21.2%) the Al (OH)

failed. After adding 70.5 g of glycine NH ₂ -CH ₂ -COOH, dissolved in 400 tti H ₂ O, and heating to 60 ° C, the precipitate dissolved again with the formation of the Al salt of the oil- amino acetic acid *

670 g of this solution was diluted with 809 ml H ₂ O and as described in Example 3 4000 g of 1 wt .- # TiO ₂ 0.8 wt -.%

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to

SiO ₂ and 2.2% by weight of Al ₂ O ₃ post-treated rutile pigments from Example 6 were added and processed to form a flowable suspension. The slurry showed a flow time of 20 seconds in the 4 mm DIN beaker and contained 7396 rutile and 0.40% by weight Al ₂ O _3, corresponding to 1.96% by weight of the Al salt of glycine based on TiO ₂ .

Example 15

250 g of taurine (NH ₂ —CH ₂ —CH ₂ —SO ₃ H) were dissolved in 800 ml of H ₂ O, 18 g of degreased aluminum tape was added and, after adding a trace of HgCl ₂ to activate the aluminum, it was completely dissolved by heating. The aluminum salt of taurine crystallized out on cooling and was dried at 120.degree. For the preparation of a concentrated aluminum salt Anatasaufschlämmung 125g of this were dissolved in 1508 ml H ₂ O and added to 4000 g as described in Example 3 untreated anatase and to a flowable suspension processes the 71 parts by weight 96 TiO ₂ and 0.40 part by weight Al ₂ 96 O ₃ corresponding to 3 _f 1% by weight of Al salt of taurine based on TiOg. The anatase suspension showed an outflow time of 13 seconds. in a 4 mm DIN cup.

Example 16

408 g of aluminum isopropylate and 366 g of sthanolamine were mixed and heated to 150 ° C. with exclusion of moisture. By the end of the reaction (after 3 to 4 hours) about half of the isopropanol formed had distilled off. The remainder was removed by drying the product in an oven at 8O ⁰ C and the Aluminiumaminoäthanolat Al (OCH ₂ CH ₂ -NH ₂₎ obtained.

a) 259.7 g of finely divided CaTiO ₅ were mixed with 100 g of HgO to form a paste containing 46.4% solids. The paste was not flowable.

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b) The experiment was repeated, with 7 * 79 of the aluminum ethanol at s (~ 5% based on CaTiO.) being added to the slurry. A thin liquid suspension with 47.1 % solids was formed immediately, which contains 0.89 % AlpO, in the form of aluminum aminoethanolate, based on CaTiO, and had a flow time of 12 seconds from the 4 mm DIN beaker.

c) The experiment was repeated with 358.5 g of CaTiO, 500 g of H ₃ O and 10.15 g of aluminum aminoethanolate. The flowable CaTiO, suspension that was formed contained 55 * 7 % solids and 0.89 % AlpO, in the form of Al-aminoethanolate based on CaTiO, and had an outflow time of 14 seconds.

Example 17

13 * 5 S degreased aluminum tape (99.9 # -ig) were introduced into a solution of 260 g of p-aminobenzenesulfonic acid in 1000 ml of water, whereupon a vigorous reaction began. Towards the end of the reaction was still so long refluxed until all reacted Al and drying at 110 ⁰ C, the aluminum salt of sulfanilic acid

Ai (, os J \ Vnh _o )

was won.

a) 347.95 g of a finely divided titanium phosphate of the composition 5 TiO ₂ .2 P ₂ O ₅ were kneaded with 300 g of water. A non-flowable, non-stirrable, firm dough with 53.7 % solids resulted.

b) The experiment was repeated with the same amounts, but an additional 3.48 g (= 1 % based on pesticide) of the above-described Al salt of sulfanilic acid were added. After a few minutes, a thin suspension was formed which

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could be easily stirred. The slurry had a solids content of 53 * 95% and contained 0.094 % Al ₃ O, in the form of the Al salt of sulfanilic acid, based on titanium phosphate. It had a flow time of 14 seconds in the 4 mm DIN cup.

c) The experiment was repeated by stirring together 493.65 g of 5 TiOg.2 P ₂ ⁰ V, 300 g of H ₃ O and 7.4 g of the Al salt of sulfanilic acid. The flowable suspension (62.6 % solids; 0.14 % Al ₂ O, in the form of the Al salt of sulfanilic acid based on titanium phosphate) had an outflow time of 20 seconds.

Example 18

From 49 ml of a basic Al nitrate solution (dissolved as Al (OH) _{2 5} (N0,) _{0 5} ), the 8l, 6 g Al ₃ O, /! contained, the Al (OH) was precipitated by adding 3.2 g of aqueous ammonia solution (21.2 μg). After adding 77.2 g of a 65% solution of bis (hydroxyethyl) methylamino-methylphosphonic acid

0 Φ
HO - P - CH ₀ - N - (CH _O - CH ₀ - 0H) ₀

\ d \ d d d

θ 0 GH,

and heating to 40 to 50 ^° C., the precipitate dissolved with formation of the Al salt of the above substituted aminophosphonic acid.

84.3 ml of this solution was diluted with 79 ml H ₀ O, and as described in Example 3 with 400 g of 1 wt .- # TiOg, 0.8 part by weight Ji SiO ₂ and 2.2 wt -.% Al ₂ O, post-treated rutile pigment from Example 6 was added and processed into a flowable suspension. The slurry exhibited a 41 seconds drainage time. in the 4 mm DIN cup and contained 71% rutile and 0.25% aigo, corresponding to 3.2 wt -.% Al-salt of bis (hydroxyethyl) methylamino-methylphosphonic acid.

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Claims (17)

Claims: $ ^ 1) Flowable, aqueous suspensions of titanium pigments or titanium fillers with a solids content of about 50 to 80% by weight , characterized in that the titanium-containing suspensions contain basic aluminum salts. . 2) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to claim 1, characterized in that they Al salts of inorganic acids with a ratio of cation to them Anion (without taking hydroxyl anions into account) from 0.5 to 5 * preferably from 1.0 to 3 * 0 *. 3) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to one of claims 1 to 2, characterized in that they contain compounds of the approximate stoichiometric composition Al (OH) ₂ , - (NO ^) ₀ , - and / or Al (OH) _{2 5} (C1) _{O 5} included. 4) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to claim 1, characterized in that that they contain aluminum salts of weak organic acids which have pK values above 1. 5) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to claim 1, characterized in that that they contain basic aluminum salts of the following general formulas a)
b). c) d)
Le A14 433 . - 23 - 409816/1127 being in the formulas R for an alkylene radical with 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as methylene (-CH ₂ -), ethylene (-CH ₂ -CH ₂ -), optionally also for a branched alkylene radical such as isopropylene (-C ( CH)) or for an arylene radical X for a simple or alkyl group-substituted oil (1-4 C atoms) Imino group (-NH-) j Y for a sulfonic acid residue (-SO. * -), a carboxylic acid residue (-COO-) or a phosphonic acid residue (-HPO, -) and Z for a simple or alkyl group-substituted (1-4 C atoms) amino group (-NH ₂ ) stands. 6) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to claim 5 *, characterized in that that they contain aluminum compounds of mono-, di-, triethanolamine, glycine, taurine and / or sulfanilic acid. 7) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to one of claims 1 to 6, characterized characterized in that the aqueous suspensions are dried in any way after their preparation and optionally to be married. 8) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to one of claims 1 to 7, characterized in that the suspensions are between 0.05 to about 3 wt. % Al ₂ O, (based on titanium compound), preferably between 0.1 to 0.9 wt -.% (based on Tltanverfalndung) in the form of basic aluminum salts. ' Le A 14 433 - 24 - 409816/1127 9) Flowable, aqueous suspensions of titanium pigments or Titanium fillers according to one of Claims to 8, characterized in that they contain rutile or anatase pigments. 10) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to one of claims 1 to 8, characterized in that they contain titanium phosphates, alkali polytitanates, Alkaline earth titanates and titanates of polyvalent metals or their mixtures contain 11) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to any one of claims 1 to 10, characterized characterized in that the suspensions are polyethylene glycols and / or polyethylene oxides with molecular weights between 4000 and 10 ^ in amounts of 0.05 to 1 wt. Ji (based on titanium compounds), preferably 0.1 to 0.5 weight percent. 12) Flowable, aqueous suspensions of titanium pigments or titanium fillers according to any one of claims 1 to 10, characterized characterized in that the suspensions are dibutylnaphthalene sulfonate and / or dinaphthyl methanesulfonate in amounts of 0.1 to 0.5 percent by weight. . Flowable, aqueous suspensions of titanium pigments or titanium fillers according to one of Claims 1 to 10, characterized in that the suspensions contain silicate fillers in amounts of 0.05 to. 5 wt -.% (Based on titanium compound), preferably from 0.1 to 1 wt .- ^ contain. 14} Flowable, aqueous suspensions of titanium pigments or titanium fillers according to one of claims 1 to 10, characterized in that the suspensions are carboxylmethyl cellulose, Hydroxyethyl cellulose and / or methyl cellulose or, alkali salts of carboxymethyl cellulose in amounts of Le A 14 453 - 25 - A09816 / 1127 0.01 to 1 part by weight Ji (in terms of titanium compound), preferably 0.03 to 0.07 wt -.%, Contained. 15) Flowable, aqueous suspensions of titanium pigments or titanium fillers with a solids content between 50 and 80% by weight , containing 0.05 to 3% by weight AlO, (based on the titanium compound), as basic aluminum salts, preferably 0.1 to 0.9 wt .- ^ Al ₃ O ₅ , and optionally stabilizers. 16) Process for the production of flowable, aqueous suspensions of titanium pigments or titanium fillers with a solids content of about 5C to 80 Oew.-Ji, characterized in that the titanium pigments or titanium fillers before, during or after suspending in an aqueous Medium mixed with basic aluminum salts. 17) Use of flowable, aqueous suspensions of titanium pigments or titanium fillers according to one of the claims 1 to 15 for the coating of paper and for the production of Disperelons paints. '/ ■ lit A 3. » Λ33 - 26 - 409816/112?