EP0258343A1

EP0258343A1 - New anticorrosive pigments, preparation and utilization thereof

Info

Publication number: EP0258343A1
Application number: EP87901433A
Authority: EP
Inventors: Manfred Gawol; Gerhard Adrian
Original assignee: Heubach Dr Hans GmbH and Co KG
Current assignee: Heubach Dr Hans GmbH and Co KG
Priority date: 1986-02-20
Filing date: 1987-02-13
Publication date: 1988-03-09
Also published as: WO1987005040A1; JPS63502597A; AU7039587A; DE3605526A1; US4840668A; DE3605526C2

Abstract

Des pigments anti-corrosifs contenant des oxydes métalliques, des phosphates métalliques et/ou du molybdate à base de métaux zinc, aluminium, fer, baryum, strontium, calcium, magnésium et titane, isolés ou associés, contiennent en outre entre 0,03 et 2% en poids de bichromate de sodium soluble ou d'une quantité équivalente de bichromate de potassium ou d'ammonium ou des quantités équivalentes des chromates ou acides chromiques correspondants. Ces pigments sont préparés par homogénéisation totale des parties chromates et ils sont utilisés comme apprêt sur des fonds métalliques ferreux ou non ferreux.Anti-corrosive pigments containing metal oxides, metal phosphates and / or molybdate based on zinc, aluminum, iron, barium, strontium, calcium, magnesium and titanium, isolated or combined, contain in addition between 0.03 and 2% by weight of soluble sodium dichromate or an equivalent quantity of potassium or ammonium dichromate or equivalent quantities of the corresponding chromates or chromic acids. These pigments are prepared by total homogenization of the chromate parts and they are used as a primer on ferrous or non-ferrous metallic bases.

Description

New anti-corrosion pigments and their manufacture and application

When pigmenting paint systems for non-ferrous metal substrates, but especially for systems and vehicles made of different metals, e.g. So far, iron, galvanized iron and aluminum have been reliant on zinc chromate and strontium chromate as active corrosion protection pigments, since only these lead to the durability of the coatings, which is particularly required on aluminum.

Attempts in these areas of application to replace the zinc chromate and strontium chromate pigments classified as carcinogenic with zinc phosphate or modified zinc phosphate pigments did not lead to the desired success.

Above all, the very good adhesion properties achieved especially by zinc and strontium chromate on various aluminum alloys under the effects of weathering have so far not been able to be reproduced with the phosphate pigments.

The object of the present invention is to develop environmentally friendly, in particular occupationally less harmful corrosion protection pigments which are able to replace zinc and strontium chromate, especially in base coats for different metal substrates.

It was found that the effectiveness of the modified basic phosphate pigments, which work optimally for iron substrates, is also effective for light metal substrates by combining them with very small amounts of soluble alkali or ammonium dichromates or chromates or

Chromic acid can be improved significantly.

These very small proportions of soluble chromate compounds or chromic acid result in a significant improvement in the adhesion and corrosion protection properties of the primers pigmented with them.

It is even possible to keep the proportion of soluble alkali or ammonium dichromates or chromic acid so low that the concentration range specified by the working substances regulation is not exceeded.

The invention accordingly relates to metal oxide,

-phosphate and / or molybdate-containing corrosion protection pigments, preferably basic metal phosphate and molybdate pigments based on the metals zinc, aluminum, iron, barium, strontium, calcium, magnesium and titanium, individually or in combination, in addition to metal oxide,

Metal phosphate and / or metal molybdate has a soluble sodium dichromate content of 0.03-2% by weight, preferably 0.2-0.6% by weight, or equivalent amounts of potassium or ammonium dichromates or equivalent amounts of the corresponding Chromates or chromic acid, based on the total weight of the pigment.

Although attempts have been made to obtain pigments with soluble chromate components by combining the phosphate pigments with zinc chromate or strontium chromate, these have only proven to be as effective as the corrosion protection pigments according to the invention, that is to say with chromate quantities, in the case of very high strontium and zinc chromate components lie higher than with the corrosion protection pigments according to the invention. -2a- Attempts to combine phosphates or oxides with chromate have been attempted for a long time. According to DE-PS 667 135 a pigment is absorbed by saturating powdery solids with aqueous solutions of chromic acid or chromates and then drying and

Get married. However, this requires approx. 25% to 53% chromic acid or chromate, based on the adsorbing solid or 20 to 35%, based on the final pigment. This is a lot that is occupationally intolerable.

In DD-PS 1082 lead chromate is struck on a carrier material. This produces insoluble lead chromate and no soluble chromate residue in amounts of 5 to 11% by weight. It is therefore known to use chromate in a firmly adsorbed or insoluble form. However, it is new and surprising that the use of very small amounts of soluble chromium compounds achieves better corrosion protection results than according to the prior art, since it has been found that higher amounts (more than 2%, in particular more than 5%) not only leach out of the soluble compound, but also increased blistering when weathering the paint films. It was therefore not obvious to reduce the known, occupationally mediocre quantities from 5% or more to quantities that are harmless or hardly objectionable in terms of occupational medicine and still achieve better results.

The combination, for example the basic metal phosphate pigments with the soluble alkali metal or ammonium dichromate or the corresponding chromate or chromic acid, has proven to be particularly effective according to the invention if it combines with the pigment sludge of the base pigment after the chemical reaction and wet confectioning are thoroughly mixed before drying, in particular using shear forces. In this way, the uniform distribution of the dissolved chromate component required for optimum effectiveness can be achieved.

The uniform and optimal distribution of the chromate component in the pigment or in a pigment combination _. n is also possible by dry mixing the components, but subsequent intensive grinding, for example in a pin, turbo or jet mill, is necessary. This preparation of the dried pigment can also be advantageous if the chromate components are added to the wet pigment before drying. In both cases, final screening to achieve fractions with certain particle sizes can be advantageous for certain applications.

A further advantageous variant of the combination of the corrosion protection pigment with the chromate components mentioned is to add pigments and / or fillers such as titanium dioxide, barium sulfate or talcum etc. to the pigment sludge before drying or the dried pigment after addition of the chromate components mentioned usually used in the formulation of primers. The pigments and filler components can also be added before the soluble chromate components are added. The amount of such additives is preferably 5 to 20% by weight, in particular 15 to 20% by weight, of the total pigment. -4- l According to a preferred embodiment, the

Pigment after the chemical reaction in the wet phase or on the dry pigment phthalic acid or phthalic anhydride in an amount of up to 10% by weight, in particular 0.3 to 3% by weight, if appropriate with heating, and then afterwards the chromate components are added, as shown in DE-AS 30 46 697 for such pigments without soluble chromium components.

Finally, the chromate content can also be made to you

Add pigment or primer third. Adequate homogenization can often be achieved when using the high-speed stirrers customary for the production of paint batches. If this is not the case, the primer can be ground with the mixed chromate components.

The following examples illustrate the invention.

example 1

100 kg of zinc oxide are slurried in a stirred tank with 800 l of water and converted into a basic zinc phosphate with 71 kg of a 75% phosphoric acid in about 2 hours.

After the wet assembly, 0.4% by weight (based on dry pigment) of sodium chromate is added to the pigment sludge before drying, and this is evenly distributed in the pigment sludge in an intensive mixer. It is then dried at 105 ° C. and processed in the usual way, for example by milling or milling and sifting. -5-

Example 2

According to Example 1, basic zinc phosphate is prepared and this is then in the aqueous slurry at a temperature of 70 - 90 ° C with an almost boiling solution of 0.8 wt .-% (based on dry pigment) phthalic anhydride and 10 parts of water for a period of 30 min. After wet confectioning, the product separated by filtration is mixed with 0.3% by weight (based on dry pigment) of sodium dichromate, this is mixed in uniformly in an intensive mixer and then the pigment sludge is dried at 105 ° C. and the dried product is then ground or marry and sighted.

Example 3

According to Example 2, basic zinc phosphate is prepared, then phthalic acid or phthalic anhydride is added in the manner described, 10% by weight (based on dry pigment) barium sulfate and 10% by weight (based on dry pigment) talc are then added and after the addition from 0.4. % By weight (based on dry pigment) sodium dichromate is mixed intensively. The pigment sludge obtained is then dried at 105 ° C. and the dried product is then ground or ground and classified.

-6-

Example 4

The basic zinc phosphate prepared according to Example 3 with barium and talc is dried (without the addition of dichromate) at 105 ° C. and, after dry preparation, 0.4 wt.% Ammonium dichromate is added in a mixer and the intensively premixed product is then added grind on a turbo mill.

The products obtained in this way with soluble alkali or ammonium dichromate or chromate components were used in the formulation described below for a primer for commercial vehicles in mixed construction on metal substrates, iron, galvanized iron and aluminum and with dry layer thicknesses of 90 - 100μm after 1200 hours tested in the salt spray test.

Recipe for 2-component coating for commercial vehicles in mixed construction with a pigment according to the invention

Gew. ^_

_ _{. Λ} parts

Component A

Epoxy resin (epoxy equivalent weight 450-525) ^'11 .2

Epoxy resin (epoxy equivalent weight 175-185) 8.4 Organically modified ontmorinonite 1.15

Wetting agent 0.17

Defoamer 0.08

Chromate-modified zinc phosphate (Example 2) 19.6

Barium sulfate (nat.) Max. 10 μm 17.0 magnesium silicate at max. 15 μm 5.4

Titanium dioxide 8.0

Methyl ethyl ketone 12.5

Xylene 10.0

Component B

Modified aliphatic polyamine 6, 5 H active equivalent equals 80

100, 0 -7-

Pigment volume concentration (PVC) in% = 39

PV / KPVK (critical pigment volume concentration) = 0.7

Solids content in% ⁼ ₇₄

For comparison, appropriate primers were made with zinc chromate and strontium chromate and tested in the same way.

An overall evaluation of the primers with the pigments according to the invention, adhesion, rust formation and blister formation being evaluated, gave practically the same results as the primers pigmented with zinc and strontium chromate.

Claims

-8th-

P a t e n t a n s r u c h e

1. Metal oxide, phosphate and / or molybdate-containing corrosion protection pigments based on the metals zinc, aluminum, iron, barium, strontium, calcium, magnesium and titanium, individually or in combination, characterized in that the pigments additionally 0 , 03-2% by weight soluble sodium dichromate or equivalent amounts of potassium dichromate, ammonium dichromate or equivalent amounts of the corresponding chromates or chromic acid, individually or in a mixture.

2. Pigments according to claim 1, characterized in that basic pigments have a striking amount of up to -. -

Contain 10% by weight, in particular 0.3-3% by weight, of phthalic acid or phthalic anhydride and dichromate, chromate and / or chromic acid is applied thereon.

3. Pigments according to claim 1 or 2, characterized in that they additionally conventional additives, other pigments and / or fillers such as titanium dioxide and / or barium sulfate and / or talc in amounts of 1 to 40 wt .-%, preferably 5 have up to 20% by weight, based on the total pigment, which are added before or after the addition of the chromatic components.

4. Pigments according to one of claims 1 to 3, characterized ge indicates that they contain 0.2 to 0.6 wt .-% soluble sodium dichromate or equivalent amounts of potassium dichromate, ammonium dichromate or the corresponding chromates or chromic acid, individually or in Mixture.

5. A process for the preparation of the pigments as claimed in claims 1 to 4 by customary chemical conversion of the metal oxides, characterized in that, after wet confectioning, the pigment sludge, before drying, contains 0.03 to 2% by weight of soluble sodium dichromate or equivalent amounts Potassium dichromate, ammonium dichromate or equivalent amounts of the corresponding chromates or of chromic acid, individually or in a mixture, are added and the mixture is homogenized and then dried and processed in the customary manner.

6. Modification of the method according to claim 5, characterized in that the pigment sludge is first dried after the wet processing and, after the processing of the dried pigment, or a pigment which is dry from the outset, 0.03 -

2% by weight of the dichromate, chromate or chromic acid components are added and then dry grinding is carried out in order to distribute the chromium components evenly. -iO-

1 7. The method according to claim 5 or 6, characterized gekennzeich¬ net that after the chemical reaction in the wet phase or with the dry pigment phthalic acid or phthalic anhydride in an amount up to 10 wt. -%, in particular

5, 0, 3 to 3% by weight is applied to the pigment, if necessary with heating, and the chromatic portions are then added.

8. The method according to one or more of claims 5, 6 0 or 7, characterized in that after the manufacture of the pigments, these, gegsbenaifalls with the addition of additives, in the wet phase or in the dried state, other pigments and / or fillers, in particular titanium dioxide and / or barium sulfate and / or talc in amounts of 1 to 40% by weight, preferably 5 to 20% by weight, are added before or after the addition of the chromate components and after the intensive mixing of the components, the preparation of the mixture, if appropriate with drying and / or thorough grinding, is carried out.

9. Use of the anti-corrosion pigments according to claim 1 to 4 for pigmentation in primers for iron and non-ferrous metal substrates or for coatings for commercial vehicles in mixed metal construction.

2510. Use according to claim 9 in primers ^" for different metal substrates, in particular iron, galvanized iron and aluminum, which, according to the pigment proportions used for the pigmentation, soluble dichromates or chromates or chromic acid, individually or

30 in the mixture, according to claims 1 to 4, in particular a proportion of soluble sodium dichromate between 0.0075 and 0.5% by weight in the case of 25% concentration or equivalent amounts of the other chromate components according to claim 1 individually or in a mixture.

35 -w- 11. Use of soluble sodium dichromate in a

Quantity of 0.03-2% by weight or equivalent quantities of potassium dichromate, ammonium dichromate or equivalent quantities of the corresponding chromates or chromic acid to increase the adhesive strength and corrosion protection effect of primers based on metal oxide, -phosphate and / or molybdate-containing corrosion protection pigments based on the metals: zinc, aluminum, iron, barium, strontium, calcium, magnesium and titanium, individually or in combinations.