DE1196309B - Reactive lacquers for metals - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C09d

German class: 22 g -7/02

Number: 1196 309

File number: D 29384IV c / 22 g

Registration date: November 18, 1958

Opening day: July 8, 1965

It is known to use mixtures for painting metals, which essentially consist of monomeric and polymeric methyl methacrylate. Such paints have a good hardness and have a high gloss, but their metal adhesion is unsatisfactory.

In British Patent 785 032, polymerization mixtures described as adhesives, putties and lacquers for copper or zinc or their Alloys can be used and as mandatory constituents a compound that is at least contains a CC double bond, curing catalysts and hydroquinone or an enolizable Acetone derivative included. According to the exemplary embodiments of this patent specification, the mixtures always with the addition of polymerized vinyl compounds, such as polystyrene, as essential components applied. These mixtures can be used as optional substances in small amounts unsaturated polyesters, acrylic acid, methacrylic acid, acrylic acid or methacrylic acid amide or their polymers, Acrylic acid esters, methyl methacrylate and polyvinyl ether are added as internal plasticizers. The constituents of such mixtures to be used optionally can be exchanged as desired. Rapid hardening of the mixtures can only be achieved with simultaneous use of the customary catalyst systems Use of the Trommsdorffectes can be achieved, d. that is, there must be a sufficiently large proportion of polymer be present in the mixture. Due to this large polymer content, however, it is not straightforward It is possible to give the mixtures a low-viscosity or sprayable, spreadable or immersible consistency without having to do without to give a quick hardening.

From the German patent specification 1 014 254 adhesives have become known, which are composed of mixtures of unsaturated polyesters, polymerizable acrylic or methacrylic acid esters, curing catalysts and polyvinyl ethers compatible with the polyester, in particular polyvinyl methyl ether, exist. As catalysts for such mixtures per compounds, preferably together with tertiary Amines or aminosulfones, optionally in the presence of cocatalysts, such as compounds with a mobile halogen atom and / or heavy metal compounds are used.

It has now been found that a polymerizable solution of essentially unsaturated Polyester resin and polyvinyl methyl ether in a lower aliphatic ester of acrylic, methacrylic or ethacrylic acid, preferably methyl methacrylate, after adding a known one Reactive lacquers for metals

Applicant:

German gold and silver refinery

formerly Roessler,

Frankfurt / M., Weißfrauenstr. 9

Named as inventor:

Dipl.-Chem. Dr. Erich Bäder, Hanau / M.

Curing catalyst can be used as a reactive paint for metals or as a primer for paints.
Adhesive compositions for painting metal surfaces have become known which consist of mixtures of unsaturated polyesters with polymerizable compounds such as methyl methacrylate and styrene. However, these mixtures do not contain any additives of polyvinyl methyl ether. On the other hand, a process for the production of moldings from polyester resin compositions which contain polyvinyl ether has become known. However, this previously known method does not suggest using the polyvinyl ethers mentioned as additives in the production of moldings for the production of reactive paints, because moldings can be compared even less with reactive paints than metal adhesives. In the production of moldings, it is important to use such mixtures,

which remove an easy removal of the manufactured articles from the metal mold. So it depends to avoid an increase in metal adhesion. In addition, according to this previously known method the polyvinyl ethers used quite commonly.

It is not necessary to use the hydrophilic polyvinyl methyl ether exclusively. After this Prior art methods, it is also necessary to use such a polyvinyl ether, its Solubility is at most 30%. This is the only one used in the present invention Polyvinyl methyl ether not fulfilled.

In general, it is advisable to prepare the reactive lacquers in such a way that the liquid components of the mixtures are more than 50%. In some cases it is advantageous to use up to 80% of the liquid to increase. The selection of the amount of liquid portion depends on the size of the portion of thread

509 599/377

3 4

Add pulling and difficult to apply solid substances. Appropriately, these substances should only

in the mixture. It is often also advisable to use the Kon- in small amounts, preferably up to 15% by weight

consistency of the mixtures by adding not a percentage of the total mixture

polymerizable solvents such as ethyl acetate.

Butyl acetate, toluene, acetone, etc. to change. In general, however, these additives should not exceed 10 to 15% of crosslinking monomeric compounds, such as. The above-mentioned Mög glycol dimethacrylate, allyl methacrylate, diallyl phthalichities, the reaction latent according to the invention, triallyl cyanurate, etc., can be added,
varnishes with regard to their brushing, dipping or spraying The variation of the proportions of all beviskosity components makes it possible to adapt a reactive varnish to the special application needs. which is specific to the respective purpose

Such unsaturated polyesters are preferred.

Resins under consideration, which have a relatively high

The reactive lacquers according to the invention have a proportion of double bonds and is essentially advantageous

borrowed from short-chain aliphatic polyvalent 15 as a primer for other paints, in particular

Alcohols, e.g. B. glycol, and short-chain, multilayer known reaction lacquers, for example based

unsaturated acids, e.g. fumaric acid or unsaturated polyester resins and styrene.

Maleic acid. In addition, this also makes it possible to modify the properties of the

certain proportions of higher dicarboxylic acid, e.g. B. Adipin- known lacquers or reactive lacquers with the-

acid or phthalic acid, as well as "higher glycols, so those of the reactive lacquers according to the invention too."

z. B. hexanediol, be incorporated. The polyvinylmethy- combine. Such primers can be

there is more in that. Mixture, preferably in quantities, white quantities of different types and colors

from 1 to 30 ^e / ö> available. In addition to the three pigments must be added. They stand out alongside

Necessary components can have even more mono their particularly high adhesion to the metal

mer and polymeric compounds in the reaction 25 through a smooth surface, which is optionally through

paints contain SeIn ₁ z. B. other methacrylic acid wet grinding can be further improved from. the

or acrylic acid esters such as butyl methacrylate. On poly- further layers of lacquer can be applied to the primer

Small amounts of polyvinyl acetate and poly can be applied without difficulty. It is here-

vinyl chloride, ketone aldehyde resin, etc. added if not required, the primer completely

will. For other purposes, it is further advantageous to allow 30 to harden. Wet on wet can also be advantageous

Fillers such as slate flour, barium sulfate and fine-tuned.

distributed SiO ₈ and the like _{} to be} mixed in. The additions A pretreatment of the metal to be painted

small amounts of paraffin are also possible. is generally not required, but it is

The processing and hardening times of the new, expedient, generally customary, grease, oil and reactive lacquers can be thoroughly removed by the choice of measures known per se.
to anything between a few minutes and several.
Hours vary. For quick setting in a room example!
temperature come preferred the combinations 1.3 mm thick sheet iron strips are at Raumvonaromatic tertiary amines and / or "-Amino- 4 ° temperature for 20 minutes with a 20% salt sulfone with organic peroxides, z. B. Benzoylper- acid, which contains a saving stain, treated. The Streioxyd, in question. Compounds that can be used as promoters are then coated with a reactive varnish with mobile halogen atoms and / or small amounts of the following composition: 64.7 parts by weight of a heavy metal compound are added to these catalyst parts of methyl methacrylate, 7.0 parts by weight of unsaturates. In addition, however, 45 saturated polyester resin, 27.0 parts by weight polyvinylmem with peroxides alone, under certain circumstances using ethyl ether, 1.0 part by weight diisopropyl-p-toluidine, with early application of heat, can also be cured. 0.3 parts by weight of paraffin, 3.0 parts by weight of a hardening

Reaction lacquers of the above type harden when put together, consisting of 50 percent by weight of benzoyl

give in a short time. For their storage peroxide and 50 percent by weight dibutyl phthalate.

It is therefore advisable to make two separate mixtures.

gen here, the first part being the binder and within 20 minutes. The test with the Erichsen

If necessary, the reducing proportions and Cokataly cupping device shows after a storage of six

Sators of the redox system contains a spherical penetration depth during the second days at room temperature

Mixture, the »hardener paste«, the peroxidic Ka- up to the flaking of the lacquer layer of 12 mm. Here-

catalysts and optionally a-aminosulfones, distributed 55 when the sheet breaks. Same result

in a solvent or plasticizer. is achieved when the painted metal strips are

Shortly before or during the painting, they are then additionally stored for 1 hour at +100 ⁰ C,

both mixtures are intimately mixed and the adhesion in a cross-cut test was in

painting metal applied. both cases very well.

The paints according to the invention are distinguished by 60.

excellent metal adhesion and by high example 2

Shine off. The burst on the metal also in Example 1 is repeated; however, the reaction contains

sharp kink not off. tion varnish additionally 30 parts by weight of barium sulfate and

It has also been found that it can increase the 1 part by weight of iron oxide to 100 parts by weight of the

Surface hardness and to improve the water mix. The penetration depth according to E r i C h s e η is

strength advantageous. is, the invention carries in this case 8 mm after both bearings.

Mixtures additionally at least one vinyl compound The adhesion in a cross-cut test was also

Chemicals such as styrene, vinyl acetate, and the like, which are also very good.

Example 3

Example 1 is repeated; However, the paint has the following composition: 49.2 parts by weight of methyl methacrylate, 10.0 parts by weight of vinyl toluene, 15.0 parts by weight of unsaturated polyester, 25.0 parts by weight of polyvinyl methyl ether, 0.5 parts by weight of diisopropyl-p-toluidine, 0.3 parts by weight paraffin, 3.0 parts by weight hardener paste.

The depth of penetration according to Erichsen is 8 mm in both cases. The liability in a cross-cut test is again very good.

Example 4

For comparison, the procedure is as in Example 1, but with the difference that the polyvinyl ether is omitted and replaced by methyl methacrylate.

A film that is about 300 μ thick does not harden. Overnight is practically the total evaporated to a thin, wafer-thin layer of less than 10 μ.

In contrast, a 20 g batch in a small dish about 40 mm in diameter is hard overnight.

Claims (1)

Claim: Use of a polymerizable solution of substantially unsaturated polyester resin and polyvinyl methyl ether in a lower aliphatic ester of the acrylic, methacrylic or Ethacrylic acid, preferably methyl methacrylate, after adding a known one Curing catalyst, as a reaction paint for metals or as a primer for paints. Considered publications:
German Auslegeschriften Nos. 1 008 487, 1 014 254; French Patent No. 1,075,226;
British Patent No. 785 032. 509 599/377 6.65 © Bundesdruckerei Berlin