CS235887B1 - Grain anticorrosive pigment and method of its production - Google Patents

Abstract

Core anticorrosive pigment based inorganic gigments and fillers from 70 to 92.5% by weight of the titanium core whites, ferric pigments, silicates aluminum and alkaline earth, sulfate barium, silica, mica, zinc white, litopone, alkaline carbonates earth and magnesium, talc, leaf hematite and from 2.5 to 30% of the coating formed zinc, calcium phosphates, of manganese and aluminum. The coating precipitated to the surface of soluble or insoluble with alkali phosphate or phosphate ammonium and phosphoric acid at pH 6-7 filtered, washed, dried at temperature 110-160 ° C and slowly. This core pigment is enhanced Inhibitory effect mainly in the initial and the final phase of corrosion and substantially reduced the cost of raw materials in production and is applicable to all types of corrosion protection of paints.

Description

The present invention relates to a zinc phosphate core anticorrosion pigment containing calcium, magnesium, manganese and aluminum phosphates.

This new type of high performance core anticorrosion pigment was developed based on the experience of developing a core anticorrosion pigment with zinc phosphate according to Qubomktlo *** & * * sm, *> / c ·, a core anticorrosion pigment with manganese phosphate according to 40 and AG 184 170 Inhibitory pigments based on zinc phosphates.

The zinc phosphate core pigment has good inhibitory properties. However, it is characterized by less activity in the initial and finally phase of the protective system.

The best solution is to combine zinc phosphate with selected more soluble and less soluble calcium, magnesium, manganese and aluminum phosphates.

In the initial phase of the protective action, calcium phosphates of CaHPG.sub.5G.sub.2, MgHPO.sub.2B.sub.2 G, were well-proven for the sustained and late phase of the protective effect, the less soluble manganese phosphates In.sub.2 / PG.sub.2 / g.sub. of aluminum AlP © ^.

Core anticorrosive pigments treated with a mixture of zinc, calcium and manganese phosphate showed the most effective inhibitory properties. However, it is possible to partially or completely replace calcium phosphate with magnesium phosphate and manganese phosphate aluminum phosphate while maintaining good inhibitory properties.

The carrier substances forming the core of the anticorrosion pigment are inorganic pigments and fillers, for example titanium dioxide, iron oxide, silica, zinc oxide, lithopone, aluminum, alkaline earth, alkali metal, calcium, magnesium carbonates and mixtures thereof.

- 2 235 887

According to the invention the surface treatment of inorganic pigments and fillers zinc phosphate-containing phosphates of calcium, magnesium, manganese and aluminum with a composition of 40% ZnO, CaO or MgO 16%, MnO or ^I2 ° 3 4? 2θ5 40%. This composition corresponds to the molar ratio of the components 1 PgO ^ ^{: 1 8 8 Ζη} θ ^{1 1} GaO ^net : 0,2 MnO or A ^ O ^ zinc is not only given by the above ratio, but is within a wider range of molar ratios of 1 ^ 2 ^ 5 ^: 2.8 ZnO: 0.3 to 2.8 CaO or MgO: 0.05 to 0.5 MnO or AlgGy the precipitated anticorrosive substances on the surface of the carrier substance are 5 to 30%, preferably 10 to 15% by weight of the core pigment ·

The production process is relatively simple and two technological processes can be chosen according to the chemicals used!

a) The pellet is dissolved in water at a temperature of 50 to 50 ° C to a concentration of 50 to 300 g / l. calcium or magnesium, and manganese or aluminum salts, then an equivalent amount of solution is dosed over 60 to 90 minutes at constant temperature; sodium phosphate or phosphoric acid and alkaline hydroxide up to a pH of 6.5 to 7.5. After 30 minutes, the suspension is filtered, washed, dried at a temperature of up to 160 ° C and ground.

b) A suspension of a weighed amount of zinc oxide, calcium hydroxide or magnesium carbonate, and manganese carbonate or oxide is metered into the suspended carrier suspension according to process a); aluminum hydrate. Thereafter, an equivalent amount of 40H ' ' ' ' ' ' The final pH is adjusted to 6.5 to 7.5. The next procedure is the same as for point a /.

In particular, the progress achieved by the invention is to increase the inhibitory effect of the core anticorrosion pigment with non-phosphate phosphate, especially in the initial and final stages of corrosion, and to reduce the cost of raw materials in its manufacture. The invention is applicable to virtually all kinds of coating compositions. Compared to conventional inhibitory pigments based on lead oxides, chromates and zinc phosphate, a saving of 50 to 80% of anticorrosive substances is possible.

- 3 Example 1

235 887

100 g of anatase titanium dioxide is decanted with stirring at 60 ° C to a volume of 330 ml in desalinated water and 13-1.6 ml of a 100 g ZnSO4 / 1 solution of zinc sulphate, 131.1 ml of calcium chloride solution are added. concentration of 50 g CaGlg / l and 12.1 ml of 100 g MnSO4 / l. Thereafter, 451.2 ml of the solution was uniformly dosed over 10 minutes into sodium phosphate decahydrate at a concentration of 10 g g / l. 12H ₂ Q / 1st After centrifugation, the suspension is stirred for a further 15 minutes, then filtered, washed with desalinated water, dried at a temperature of up to 160 ° and ground. The white anticorrosive pigment contains 9.75% Zh ^ / PO ^ / g · 211.0,

4.32% CaHP0 _fourth 2 ^ 0 and 0.93% Mn ₃ / PQ _4/2. 3 ^ 0.

Example 2

100 g of thermic ferric red are melted under stirring at 60 ° C to 330 ml in desalinated water and a suspension containing 6.63 g of zinc oxide, 2.19 g of calcium hydroxide and 0.77 g of manganese carbonate is added »The suspension is heated mix for 80¾ and 15 minutes. It is then dosed uniformly over 90 minutes

17.3 ml of 40% phosphoric acid. After the addition is complete, the suspension is stirred for a further 15 minutes, adjusted to pH 7 with alkaline hydroxide, filtered, washed well with desalinated water, dried at a temperature of up to 160 ° C and ground.

The color anticorrosive pigment contains 9.75% Zn ^ / PQ ^ g · 2 ^ 0,

4.32% CaHPO ₄ . 2 ^ 0 and 0.93% Mn ₃ / P0 _4/2. 3 ^ 0 »

Example 3

100 g of kaolin are stirred under stirring at 60 ° C to 330 ml in desalinated water, a suspension containing 6.63 g of zinc oxide, 2.8 g of magnesium carbonate and 0.46 g of aluminum oxide is added, the suspension is heated to 80 ° C and stirred for 15 minutes. 18.8 ml of 40% phosphoric acid are then metered in uniformly over 90 minutes. After completion of the dosing, the suspension is stirred for a further 15 to 20 minutes and adjusted to pH 6.5 to 7.5 with alkaline hydroxide, then filtered, washed in desalinated water, dried at-do to 160 ° C and ground.

Anticorrosive pigment contains 9.75% Zn ₃ / P0 _4/2 · 2 ^ 0, 4.32% MgSP0 _fourth 2 Hgo _{and 0> 93} % A1PO ₄ .

- 4 Example 4

The procedure of Example 1, except that barium sulfate is used.

235 887 that instead of titanium white

The white anticorrosive pigment contains 9.75% Zn ^ / PO ^ / ^ · 21 ^ 0,

4.32% CaHP0 _fourth 2 ^ 0 and 0.93% Mn ₃ / _PO4 / _2. 3H ₂ 0.

Example 5

The procedure of Example 2, except that silicon dioxide was used in place of the thermic, cesium red.

The white anticorrosive pigment contains 9.75% Zn (R) / PQ (R). 2 ^ 0,

4.32% CaHP0 _fourth 20% and 0.93% MnTO4g. 3 ^ 0.

Example 6

The procedure of Example 3 except that mica was used instead of kaolin.

Anticorrosive pigment contains 9.75% Zn ₃ / P0 _4/2 · 2H ₂ 0, 4.32%. 2H ₂ o and 0.93% AlPO ₄ .

Example 7

The procedure of Example 1 except that zinc white was used instead of titanium white.

White anticorrosion pigment contains 9.75 _3% Zn / _PO4 / _2. 2H ₂ 0,

4.32% CaHPQ ₄ . 2 ^ 0 and 0.93% Mn ₃ / P0 _4/2. IHgO.

Example 8

The procedure of Example 1 except that lithopone was used instead of titanium white.

White anticorrosion pigment contains 9.75 _3% Zn / _PO4 / _2. 21 ^ 0,

4.32; % Ca0PO ₄ . 21 ^ 0 and 0.93% Mn ₃ / _PO4 / _2. 3H ₂ 0.

Example 9

The procedure of Example 1 except that chalk was used instead of titanium.

White anticorrosion pigment contains 9.75% Zn ₃ / P0 _4/2. 2H ₂ 0,

4.32% CaBP0 ₄ . 2 ^ 0 and 0.93% phon ₃ / _PO4 / _2. 3 ^ 0.

Example 10

The process of Example 2, except that talc is used instead of the red iron.

Anticorrosive pigment contains 9.75% Zn ₃ / P0 _4/2 .21 ^ 0,

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4.32% CaOPO ₄ . 2 ^ 0 and 0.93% Mn ^ P0 _4/2. 31 ^ 0.

Example 11

The procedure of Example 3 except that hematite was used instead of kaolin.

The anticorrosive pigment contains 9.75% Zh / POg. 2H ^ 0,

4.32% MgHPO ₄ .. 2H ₂ O and 0.93% Α1Ρ0 ₄ ·

Corrosion tests were carried out in an aqueous extract of a coating film with pentaeritrite alkyd binder GHSP - L65, modified with 65% linseed oil with a volume concentration of 30% OKP, for 10 days.

The test results are shown in the table in comparison with pure zinc phosphate, alkyd binder used and water. As shown in the table, pigments and fillers treated with mixed zinc, calcium, manganese, magnesium and aluminum phosphates have a very good inhibitory effect.

Table.

Example Pigment ▼ filler Corrosionin phosphate phosphate Ca Mg FeAl bicalic depletion effect ¹⁰ Aim / year%

1 titanium white 9.75 4.32 - 0,93 - 1.1 97.39 2 thermal _in irish June 9.75 4.32 «» 0.93 - 1,2 97.15 3 kaolin 9.75 - 4.32 - - 0.93 1.3 96.91 4 barium sulphate 9.75 4.32 - 0.93 - 1.6 96.20 5 silica 9.75 4.32 - 0.93 - 1, 0 97.62 6 mica 9.75 - 4.32 - 0.93 0.9 97.86 7 zinc white 9.75 4.32 «Ν» 0.93 «> 1.0 97.62 8 litopon 9.75 4.32 - 0.93 - 1,2 97.15 9 chalk 9.75 4.32 - 0.93 - 1.3 96.91 10 talc 9.75 4.32 - 0.93 1, 2 97.15 11 hematite 9.75 4.32 Μ » 0.93 0.9 97.86 «Η» zinc phosphate 1.9 95.49 - alkyd 35.8 14.96 - water 42.1  -

Claims (5)

1, core anticorrosive and fillers, characterized in that it consists of a core> β £ 43ΐ £ & 4-titanium bélobyl, iron oxide pigments, aluminum silicates and alkali ickýdi earth sulfate Burma 'silica slídiA, zinc Belot, lithopone ₈ carbonates, alkaline earth and magnesium, talc, and flaky hematite coating composed of zinc phosphate, calcium and / or magnesium, manganese and / or aluminum constituting by weight 2.5 to 30%, preferably 10 to 15% of the total weight of the core pigment, zaiimolárníha 1 ratio _of P ₅ 0: 0.2 to 2.8 ZnO: 0.2 to 2.8 CaO, MgO: 0.2 to 0.5 MnO, Al ^, preferably 1 ^ 2 ^ 5 ^{^ -NO:} ΜηΟ, Α ^Ο · 2. A process according to claim 1, wherein an aqueous solution of zinc sulfate, magnesium sulfate and / or calcium chloride and aluminum sulfate is added to the aqueous suspension 6 at a concentration of 50 to 300 g / l with stirring over 5 to 10 minutes. - and / or manganese sulphate at a concentration of 50 to 100 g / l, the suspension is heated to 60 ° C and an equivalent amount of an alkaline or ammonium phosphate solution of 50 to 100 g / l and the treated product is uniformly dosed within 60 to 90 minutes The mixture is filtered, washed, dried at a temperature of up to 110 ° C and ground. 3. A process for the production of a core anticorrosive pigment e. Filler according to claim 1, characterized in that the aqueous suspension is iD-W. 50 to 300 g / l, with agitation for 5 to 10 minutes, add an aqueous solution of magnesium sulphate, zinc sulphate and aluminum sulphate at a concentration of 50 to 100 g / l; An equal amount of an alkaline or ammonium phosphate solution having a concentration of 50-100 g / l is uniformly metered in and the treated product is filtered, washed, dried at a temperature of 110 DEG C. and ground. 4. A method according to claim 1, wherein a suspension of zinc oxide, calcium hydroxide and manganese carbonate at a concentration of 50 to 300 g / l is added to the aqueous suspension at a concentration of 50-300 g / l with stirring over a period of 5-10 minutes. 100 g / l, the suspension is heated to 80 ° C and an equivalent amount of 40% phosphoric acid is added uniformly over a period of 120 to 180 minutes, and the suspension is stirred for 30 minutes after cooling to 50 ° _C. The treated product is filtered, washed and dried at a temperature of up to 7235,887 110 ° Gaa ground. 5. A process according to any one of Claims 4 to 4, characterized in that: the calcium phosphate is at least partially replaced by magnesium phosphate and the manganese phosphate is at least partially replaced by aluminum phosphate.