DE2640427C2 - - Google Patents

Description

Catalyzing the drying process of unsaturated by atmospheric oxygen drying binders such. B. Stand oils, isomerized oils, ricinine oils, blown oils, maleate oils, styrenated oils, acrylated oils, cyclo oils, gel oils, alkyd resins, urethane oils, epoxy resin esters, oil-modified ureas or oil-modified urea and phenolic resins can by natural or artificial prooxidants take place.

Natural pro-oxidants include various companions fatty oils and organic compounds containing easily oxidizable and capable of radical formation. To These also include compounds that complex a metal atom have tied. Known artificial pro-oxidants are radicals, Peroxides or hydroperoxides, ozonides, organic salts polyvalent Metals and oxides and hydroxides of polyvalent metals.  

For the drying of unsaturated air-drying binders come in the paint and paint industry virtually table only the salts of organic acids with polyvalent metals used, which are traded in 100% form as dry solids, dissolved as siccatives. An essential component is the metal bound to a higher molecular weight acid, while the organic acid has only minor influence. As acids are mainly into consideration: naphthenic acids, α- Äthylhexan acids, oil and other fatty acids, such as. For example, linseed oil fatty acid and tall oil fatty acid, oxy fatty acids, the best known of which is castor oil fatty acid, decanoic acids and rosin acids, which include abietic acids. In addition, aromatic keto acids, aliphatic ketocarboxylic acids and xanthogenic acids, etc. are also suitable for the same purpose (see, for example, Hans Kittel "Farben-, Lack- und Kunststofflexikon" 1952, p. 760, Wissenschaftsvertrag GmbH, Stuttgart).

The oxidation process during drying, caused by Oxygen, is a natural process without further action continues to run, albeit for lacquer technology Application too slow, unless pro-oxidants, in practice Finally, siccatives are added. When increasing the used Sikkativmenge the drying process is accelerated, brings but with a shortening of the life of the film. To Low addition leads only to unsatisfactory drying, but generally longer life. The efforts, the after turn off parts when using metal cancases, against from three points of view:

• 1. Use of drying accelerators after fulfillment their function be disabled;
• 2. Use of additives that the siccative effect synergistically so accelerate that lower sikkativmengen sufficient;
• 3. Development of siccatives that have the same metal content are more effective.

Only partially, notably at point 2, could be synergistic effective zirconium compounds are found. recently are also azides and hydrazones (US-PS 12 93 719), ketones with ungestättigten residues (DE-PS 9 35 689) as a drying accelerator also known to co-use of 1,10-phenanthroline as synergistic catalyst has been described in the literature. Other efforts, for. B. the use of metal-free carotenes, did not lead to acceptable results.

The invention was based on the task, compounds Find out the effect as synergistic additives significantly increase of metal siccatives and after fulfillment their function are inactivated, the above Deficiencies so only have a very limited extent.

It has now been found that one can arrive at these results can, if considered as a synergistic substance for salts organic Acids with mono- and polyvalent metals amine oxides, as they sum in the amount required for such a resource Properties far exceed the substances used so far.

It can be assumed that the effectiveness on the loosely bound O atom is due, however, has become Surprisingly, that the increase in the effect of Initial drying is much higher than the introduced O content corresponds.

The invention relates to the use of amine oxides of general formula

in the R is a straight-chain alkyl radical, a branched one Alkyl radical, a cycloalkyl or an alkenyl radical  with 1-20 C atoms. As examples may be mentioned Dimethylhexadecylamine oxide, dimethylcyclohexylamine oxide, triethyl amine oxide and dimethyl coconut fatty amide.

Amine oxides are prepared by generally known methods from tertiary Amines by reaction with hydrogen peroxide or others Peroxide compounds produced. The inventively used Compounds lead in by atmospheric oxygen drying unge saturated binders to drastically shorter drying times, whereby the natural differences between konjuen and iso lenbindemitteln remain proportional.

A positive effect on the drying is for all in Practice used metal salts and their combinations. As is known, cobalt siccatives are present in the drying catalytic Effect at the top. Cobalt follow manganese, lead, iron, cerium, zircon Conium, barium, calcium, zinc. But also other metals like Magne sium, aluminum, vanadium, nickel, copper molybdenum, tin, tho rium and lanthanum are used. Usually used in the rarest cases one metal dryer. As every metal has certain specific properties, it seems obvious More Use metal dryers for optimum effect to achieve. Examples of common metal combinations are: cobalt-lead manganese, cobalt-lead, cobalt-manganese, lead Manganese, cobalt-zinc, cobalt-lead-zinc-manganese, cobalt-zirconium, Cobalt-cerium, cobalt-aluminum, cobalt-barium-zinc, cobalt-zirconium Conium zinc, cobalt calcium zirconium, cobalt calcium zinc, Cobalt-barium-zirconium. The quantitative range of desiccant additives to the drying unsaturated binder is preferably at:

0.03-0.1% by weight of Co
0.03-0.7 wt% Pb
0.02-0.04 wt% Mn
0.075-0.15 wt .-% Ca, Ba or Zn and
0.1-0.3 wt .-% Zr, wherein the metal contents are based on 100 wt .-% binder.

Amine oxide compounds show with both Single-metal as well as multi-metal dryers are highly synergistic Effects. Here, the drying catalytic effect is much higher as the O content of the compound corresponds, so that here a real Synergist for salts of organic acids with one and more valent metals present. It should be noted that just in the course of scarcity of raw materials rare and expensive metals only still needed to a small extent. Conversely, by the reduced use of metals with equally good initial drying a metal pollution of the environment primarily with toxic metals significantly reduced.

Interestingly, amine oxides become functional after fulfilling their function d. H. inactivated after loss of their O content, so that here despite reduced amount of metal an accelerated drying process is expected at extended life of the film and one So an old desire of the paint and paint industry met.

The amount of organic synergistic acting according to the invention Fabric required for the improvement of drying is, depending on the nature of the binder to be dried and the siccative formulation used within wide limits, usually between 0.1-5 wt .-%, based on the finished paint color, vary. Of course, higher additives may be required in general, however, 0.5-2% by weight, based on Finished lacquer.

In general, the substances to be used according to the invention incorporated separately from the siccative additive of the enamel paint, since active oxygen-containing compounds with Metallsikkativen, ins special cobalt, molybdenum, vanadium, manganese salts too unwanted Reactions that assume the violence of an explosion, being able to lead.  

Example 1

A binder is sikkativiert as follows:

100 g of oily alkyl resin based on vegetable fatty acids dissolved 60% by weight in xylene,
2 g cobalt-lead calcium octoate (= 1 wt .-% Co content, 10 wt .-% Pb content, 2 wt .-% Ca content.

Based on 100 wt .-% binder corresponds to the following Metal contents:

0.033 wt% Co
0.330 wt.% Pb
0.066 wt.% Ca.

To this blank, 0.8 g of dimethylhexadecylamine oxide was added.

The dry times are according to the ICI-Sandspur method in Blind test at 4.5 hours. By the addition of dimethyl Hexadecylaminoxid this is equivalent to 2.5 hours an improvement of ~45%.

example 2

A binder based on a long oil with resin acid poor tall oil fatty acid modified alkyd resin are first increasing amounts of cobalt octoate 1% ig added.

Herewith the following drying times are achieved:

0.0133 wt .-% Co content based on 100 wt .-% binder | 14 Std. 0.0266 wt .-% Co content based on 100 wt .-% binder 9 hours 0.0399 wt .-% Co content based on 100 wt .-% binder 6.5 hours 0.0533 wt .-% Co content based on 100 wt .-% binder 5.5 hours

Be a 0.0133 wt .-% Co offset sample

• a) 0.5 wt .-% triethylamine oxide
• b) 0.5% by weight of dimethylcyclohexylamine oxide

added.

The dry times recorded in Table 2 are obtained.

a) 0.0133 wt .-% Co based on 100 wt .-% binder + 0.5000 wt .-% triethylamine oxide 6.2 hours b) 0.0133% by weight of Co, based on 100% by weight of binder + 0.5000% by weight of dimethylcyclohexylamine oxide 4.7 hours

To achieve such short drying times with Co-Metal, would have to use ~400 wt .-% more Co.

example 3

A white enamel paint of the following composition

700.0 g of long oil low acid resin tall oil fatty acid modified alkyd resin, 60% by weight in gasoline
200.0 g of titanium dioxide (rutile type)
85.0 g of xylene
10.0 g of butyl alcohol
5.0 g of methyl ethyl ketoxime

be first
4.6 g of cobalt-barium-zinc octoate solution (1.2% by weight of Co, 7.2% by weight of Ba, 3.2% by weight of Zn)
added.

This sample will be then

• a) 0.5 wt .-% triethylamine oxide
• b) 0.5% by weight of dimethylcyclohexylamine oxide

added.

The values obtained in Table 3 are worked out.  

Table 3

The time advantage gained by the amine oxides is at ~70%.

example 4

A binder based on medium-oil Linseölalkyds is Cobalt zirconium octoate (6 wt% Co, 9 wt% Zr) was added first.

100.0 g of medium-oil linseed oil alkyd, 55% by weight dissolved in white spirit
0.5 g of cobalt zirconium octoate (6 wt% Co, 9 wt% Zr).

Become this blind attempt

• a) 0.5 wt .-% triethylamine oxide
• b) 0.5% by weight of dimethyl coconut fatty amine oxide

added.

The dry times found are recorded in Table 4.  

Table 4

The drying time gain is ~55%.

example 5

An oxide yellow paint of the following composition

700.0 g of long oil low acid resin tall oil fatty acid modified alkyd resin, 60% by weight in gasoline
100.0 g of iron oxide yellow
100.0 g calcium carbonate chalk
85.0 g of xylene
10.0 g of butyl alcohol
5.0 g of methyl ethyl ketoxime

be first with
4.6 g of cobalt-barium-zirconium octoate solution (1.2% by weight of Co, 7.2% by weight of Ba, 3.2% by weight of Zr)
added.

This sample will be then

• a) triethylamine oxide
• b) dimethylcyclohexylamine oxide
• c) dimethylhexadecylamine oxide

added in a concentration of 0.5 wt .-%.

The drying times shown in Table 5 are obtained.  

Table 5

The gain in dry season is due to the addition of Amine oxides ~65%.

Claims (2)

1. A means for improving the drying of oxidatively drying unsaturated binders in combination with salts of monovalent and / or polyvalent metals with organic acids, characterized in that they amine oxides of the general mean formula in which R is a straight-chain or branched-chain alkyl, cycloalkyl or alkenyl radical having 1 to 20 C atoms or combinations thereof. 2. Use of the agent according to claim 1 in the sikkati vation of oxidatively drying unsaturated binders, characterized in that the amine oxides in amounts of 0.1 to 10 wt .-%, preferably 0.5 to 2 wt .-% based on the binder used.