DE2012526C3 - Coating agents - Google Patents

Description

35

1.1 to more than 30 to 70 mole percent Butanediol- (1,3) and

1.2 to less than 70 to 30 mole percent of one or more other aliphatic or cycloaliphatic diols in which the hydroxyl functions are represented by 2 to 8 carbon atoms are separated and can optionally be in place of up to 2 of the carbon atoms, oxygen atoms, which in turn by at least 2 carbon atoms from each other and from the hydroxyl functions should be separated, with 1,4-bis (hydroxymethyO-cyclohsxan is excluded

consists, and mixture II

Π.1 to 91 to 50 mol percent of one or more aromatic or cycloaliphatic Dicarboxylic acids and / or their derivatives and

II.2 to 9 to 50 mol percent of one or more aliphatic dicarboxylic acids with 4 to 12 carbon atoms and / or their derivatives

consists.

2. Coating agent according to claim 1, characterized in that linear polyesters are used are, for the preparation of which a mixture I has been used, the 50 to 70 mol percent The invention relates to liquid coating compositions based on a mixture of binders and organic solvents or water and the binder water-solubilizing additives or optionally also on a solvent-free basis, which acts as a binder

A. 50 to 10 percent by weight aminoplasts and / or their low molecular weight defined precursors and

B. 50 to 90 percent by weight of hydroxyl-containing and carboxyl-containing polyesters aliphatic diols and optionally other diols on the one hand and aromatic and aliphatic ones Dicarboxylic acids, on the other hand, in addition to optionally customary auxiliaries

contain, the binder also by co-condensation of aminoplasts and / or their low molecular weight precursors with the polyesters or through mixed condensation of the starting materials the aminoplast production can have been made with polyesters.

A large number of coating agents are known which, as binders, are mixtures of aminoplasts and Contain polyesters or so-called plasticized amino resins. So is from the German patent specification 1 015 165 known by curing a mixture of a phthalic acid-fumaric acid-propylene glycol polyester on the one hand and a butylated melamine-formaldehyde resin on the other hand coatings to manufacture. The paint films obtained have a low chemical resistance.

From the German patent specification 1015165 is also known that one receives extremely chemically resistant coatings if one alkylated melamine-formaldehyde or urea-formaldehyde condensation product combined with a linear polyester made by polyesterification

a dicarbo acid with a diol of the general and therefore only applicable with great effort and Formula also lead to overcoats that by no means

u iOR) O— f '' ~ ^{> x} - A- ^ _O-iRO \ H ⁵³⁶⁵ ^ ^1- as coverings made from conventional raw materials

5 From UK Patent Specification 676,372

in <i _w λ «n 1 au, π j ·. ,

Sih2 £> Lome «ä ££ W ^ £," * ^{£ lektrois} ° ^ <* e, especially wire enamel based on 4 carbon atoms means, R for _em Alkl

ome «ä ££ W ^ £,,

tomen means, R for _em alkylene of polyesters from terephthalic acid, aliphatic

ßdjkalmit ^ b.saK ^ dicarboxylic acids and ethylene glycol known, the

each werngstenslsmdundd ^ Summevonmundn possibly with other synthetic or

no larger than 3 st. The dabe, won over _lo natülih Hd h Ailh

jewe ^ ndn y

no larger than 3 st. The dabe, obtained exceeds _lo natural resins, including aminoplast resins, _Z ights are hard but very brittle ( "before encryption can be combined. These polyesters have gleichsbeispiei ¹ I a molecular weight of 10 000 to more, and

_In the USA Patent No. 2460 186, poly- are crystalline. Wey WQta ^ Z d.e_ application dissolved ₁₅ dilute solutions, while at | therefore these polyesters of relatively außei be sungsmitteln in Löester from 2-A_thyI-hexane _£ pick-up (3 l) as a plasticizer, such as phenols or cresols, the wire in urea-formaldehyde or melamine-formaldehyde varnish is common, with normal sheet metal varnishing hyd-condensation products are described; Which, however, are undesirable.

The coatings obtained from this information are admittedly to the _fn Houben-Weyl, “Methods of organizing

Partly stretchable and impact-resistant, but too soft (see niche chemistry ”, Vol. 14/2, pp. 21, 22, 29, 337, 338, comparative example 1) ... ao 362 (1963), the production of linear polyesters

In addition, our own experiments show in which, as well as the possibility of their crosslinking, very general mixtures of linear polyesters and a melamine mine are described. Specific recipes, or which formaldehyde resin have been cured, so that the coatings obtained in this case, advantageously used, are stretchable, but should become soft, are not specified.
(see Comparative Examples 3 and 4) _{f 25 In the äkeren} p _{atentanmeIdung (eng} disclosure tsche

In French patent specification 1 574 618, application specification 1 807 778) describes high molecular weight poly coating agents which describe aminoplasts and esters as binder components which contain linear polyesters, the composition and properties of the diol component not being at least 70 mol percent with that of the linear polyesters products according to the invention match,
consists of 1,4-bis (hydroxymethyl) cyclohexane. These 30 In the older patent application (German open coating agents deliver hard and at the same time very detailed specification 1 954 678) are binders for overclastic coatings. The good properties of the trains described, which consist of a polyester and one of these French patent coatings obtained aminoplasts. In contrast to the present situation, the high content of the invention is based on pulverulent and linear polyesters of 1 ABis-hydroxymethyO-cyclo- 35 non-liquid products. In this case, hexane is attributed to the publication, which, however, cannot be inferred to a large extent as to the extent to which the composition and expenditure can be produced and is therefore expensive. Molecular weight has an influence on the phase of the product

In the German Auslegeschrift 1 101 667 will have. In addition, the products contain over solvents free stoving enamels based mainly on aminoplasts.

Aminoplasts are described, which are thereby obtained. Plasticizers containing hydroxyl groups are described as particularly suitable plasticizers containing hydroxyl groups. As the only example taken from plasticizers, such as. B. castor oil, called; 45 can be used, but also hydroxyl group-free softening of branched polyesters with carboxylic acid generators, such as petroleum distillates or common phthalate-modified aminoplasts. The use of plasticizers is used. The from such over-butanediol (1,3) is not described,
Covers produced by stoving traction means. The invention is based on the object of

have only low solvent resistance and low cost chemicals, coatings Resilience to, poorly adhere to places where there is high elasticity with great on metals and, moreover, have unsatisfied- hardness unite.

low mechanical properties. This task was surprisingly solved by

German Patent 1,231,833 has found that coating agents are found in which it is also known that linear polyesters with average MoI-benen coating agents of the German Auslegeschrift weight between 250 and 25CO are used from the above-described component B, 1101 667 by Addition of hardeners, including cold-curing agents, which can be produced by esterification of mixtures I and II. An adjustment has been made, with mixture I
This improves the coating properties

not reached. 60 1.1 to more than 30 to 70 mol percent from butane

From the German Offenlegungsschrift 1 595 857 diol- (1, 3) and

special aminoplasts are known that can also be used in

Solvent-free form can be used. 1.2 to less than 70 to 30 mole percent of one The coating films produced from it are hard, or several other aliphatic or cyclo-

but very brittle and inelastic. Also combinations 65 aliphatic diols in which the hydroxyl ions these special amino resins with common functions are formed by 2 to 8 carbon atoms

Coating resins should be processable without solvents, are separated and, if necessary, instead of up to

However, such mixtures are very highly viscous 2 of the carbon atoms are oxygen atoms

can, which in turn by at least 2 carmethyl, diethyl or dipropyl esters, werlenstoffatome used from each other i «pd from the hyde. If the dicarboxylic acids form anhydrides, droxyl functions should be separated, these can also be used, for. B. Hexa-1,4 - Bis (hydroxymethyl) - cyclohexane taken from hydrophthalic anhydride, tetrahydrophthalic acid taken is, 5 anhydride, succinic anhydride, glutaric acid

anhydride or maleic anhydride. In this case, phthalic anhydride is preferably used and mixture II.

It has proven to be advantageous if the acid

11.1 91 to 50 mol percent of one or more components II consists of 60 to 80 mol percent of II.1 aromatic or cycloaliphatic dicarbonio and 20 to 40 mol percent of II.2,
acids and / or their derivatives and coatings with particularly good properties

when using linear polyesters with

11.2 to 9 to 50 mol percent from one or more average molar weights from 600 to 2000, the over-aliphatic Dicarboxylic acids with 4 to 12 carbons contain predominantly hydroxyl groups, i.e. with one Ienstoffatomen and / or their derivatives 15 molar excess of diol have been produced.

When using polyesters that are aliphatic

consists. . Dicarboxylic acid succinic acid or its anhydride

contain, those with average molecular weight below average molecular weight is preferred in the range between 700 and 2000,
of the present invention is the number average of 20. The production of the polyesters can be according to all known and customary processes, with or without. Catalyst, with or without passing through an inert

As concomitantly used diols in which the hy- gas streams, as solution condensation, molten condroxyl functions by 2 to 8 carbon atoms densation or azeotrope esterification, are separated at temperature and optionally up to 2 of the 25 doors are carried out up to 250 ° C or higher, carbon atoms are replaced by oxygen atoms where the released water or the free, which in turn are continuously removed by at least 2 carbon-becoming alkanols, material atoms from each other and from the hydroxyl The esterification proceeds almost quantitatively and can be functions should be separated. B. by determining the hydroxyl and acid numbers ethylene glycol, propanediol (1,2), propanediol (1,3), 30 can be followed. As a rule, the esterification butanediol (1,2), butanediol (2,3), butanediol (1,4) conditions are chosen so that the reaction 2,2-dimethyl-propanediol (1,3 ), Hexanediol - (1,6), is as complete as possible, ie until the acid number in 2-ethylhexanediol (l, 3), cyclohexanediol (1,2), cyclo-polyester approaches from η mol of diol and (11 - 1) Mol of hexanediol (1,4), 1,2-bis (hydroxymethyl) cyclohexane, dicarboxylic acid is less than 7 mg KOH / g. In Anl, 3-bis (hydroxymethyl) cyclohexane, *, 8-bis- (hydroxy- 35 sets of η mole of diol and (n + 1) moles of dicarboxylic acid methyl) tricyclo [5,2, l, 0 ² ' ^e ] -decane, where χ for 3, 4 is esterified until the hydroxyl number is below 7 mg or 5, diethylene glycol, triethylene glycol, di-KOH / g is. The molecular weight of the polyester can be propylene glycol or tripropylene glycol. Cycloalipha- in a simple manner on the use ratio of Diol tables Diols can regulate in their cis or trans form and dicarboxylic acid. It goes without saying that they can be used or as a mixture of both forms. The use of ethylene glycol and / or propanoic acid between the mentioned limit values diol- (1.2) is preferred. lie. In these cases one has to pay attention to

As aromatic or cycloaliphatic Dicarbon- that the condensation in time, ie when reaching acids are z. B. phthalic acid, isophthalic acid, tetra of the desired molecular weight, terminated hydrophthalic acid, hexahydrophthalic acid, hexa- 45 is. So it is possible, for example, from η mol of diol hydroisophthalic acid and endomethylene or and η mol dicarboxylic acid linear polyester hcrzu-endoethylene-tetrahydrophthalic acid, hexachlorendo sites that contain on average equal amounts of carboxylmethylene-tetrahydrophthalic acid or tetrabromo and hydroxyl groups,
Phthalic acid suitable, with the cycloaliphatic The esterification temperature is chosen so that

Dicarboxylic acids can be used in their trans- or cis-form or as a mixture of both forms to reduce the loss of volatile substances. remain, ie, at least during the first time-The use of dicarboxylic acids in which the esterification area is esterified at a temperature of carboxyl groups in the 1,2- or 1,3-position which are below the boiling point of the lowest , in particular of phthalic acid and hexa-boiling starting substance,
hydrophthalic acid, is preferred. 55 When manufacturing the polyester, it is important to

Suitable aliphatic dicarboxylic acids are both the molecular weight of the polyester and especially succinic acid, glutaric acid, adipic acid, the composition of which influences the properties of suberic acid, Sebacic acid, decanedicarboxylic acid or ten of the paint films produced therefrom. at 2,2,4-trimethyl adipic acid. But it can also usually have higher mean molecular weights Unsaturated dicarboxylic acids such as Ma- 60 reduces the hardness of the paint film, while the oleic acid, fumaric acid, itaconic acid or citracon elasticity increases, on the other hand, with lower molar acid, can be used, but the use will weigh the flexibility of the paint film in the case of equally saturated aliphatic dicarboxylic acids with an increase in hardness of 4 or more times. In a similar way 6 carbon atoms, especially adipic acid, also affect differences in the composition Succinic acid or a 1: 1 mixture for the 65 breakdown of the polyester: If there is a higher proportion of Acids, preferred. aliphatic dicarboxylic acids and with larger chain

Instead of the free dicarboxylic acids, the length of the aliphatic dicarboxylic acids can also be used their esters with short-chain alkanols, e.g. B. Di-elasticity of the paint film, while its hardness

is decreased. Conversely, with increasing formaldehyde, the approach is added, with it being a self-part of aromatic and / or cycloaliphatic !! understandable is also possible, additionally usual Dicarboxylic acids in polyester, the paint film of harder alcohols to modify the plasli- and less flexible. A similar influence is to be used with the above-mentioned amino resins. The memos to be used other diols from: With increasing methods for the production of such plasticized amiamenders Chain length of these open aldehyde resins used both for solvent-based ails chain diols and, with increasing proportions, also for aqueous paint systems are known; one these diols in the polyester will soften the paint film and more flexible. If one uses, however, to find literature (compare e.g. Houben - Position of the polyester additional diols with very short io W e y 1, Methods of Organic Chemistry, 4th AuIl., and branched carbon chains or with cyclo- Vol. 14/2, p. 319ff., Georg-Thieme-Verlag, Stuttgart, aliphatic rings, then those from these poly- 1963, or Ulimann's Encyclopedia of Technical estern produced lacquer films usually with additional chemistry, 3rd ed., vol. 3, p. 475ff., Urban & Schwarzcnnahmendem Share in these diols harder and berg, Munich, 1953).

less elastic. If these rules are known, it is 15 to combine with those according to the invention Difficulties are possible; a large number of commercially available polyesters are available in the context of the polyester used Claimed area of polyester with for the respective aminoplast or their defined precursors; ture Purpose of use optimal properties available.

choose and for the coating according to the invention although very low molecular weight linear polyesters

to use funds. *> in combination with the low molecular weight, defi-

As suitable aminoplasts, the known nated precursors of aminoplasts can also be used without reaction products of aldehydes, in particular solvents, are usually initially group-bearing substances for formaldehyde, with several amino or amido production of the coatings in question, such as. B. with polyester and aminoplast or its defined melamine, urea, dicyandiamide and Benzoguan- * $ precursors or the plasticized amine-aldehyde resin amine. The aminoplasts are particularly suitable in conventional lacquer solvents, such as, for example, in particular the amino-propanol, iso-propanol, butanol, ethyl acetate, butyl plastics modified with alcohols. acetate, ethyl glycol, ethyl glycol acetate, butyl glycol,

Because of the limited compatibility of methyl ethyl ketone, methyl isobutyl ketone and cyclodieser Resin-like products with the hexanone, trichlorethylene or mixtures according to the invention to be used in various ways Polyesters are preferably dissolved in such solvents. It's self-depleted molecular, defined precursors of amino- also possible and economical plastic, which is recommended for the reasons to be used according to the invention, more or less large Polyesters are practically indefinitely miscible, some less polar solvents, such as. B. set such defined precursors of amino benzene, toluene, xylene or higher-boiling aromatic plastic are z. B. Tetramethylolbenzoguanamine, tri-sections, also to be used. The amount of methylolmelamine or hexamethylolmelamine, which is within these less polar solvents also in partially or completely etherified form, e.g. B. the solubility of the inventively used as tetrakis- (methoxymethyl) -benzoguanamine, tetra-polyester and their compatibility with the einekis- (ethoxymethyl) -benzoguanamine or polyether of the 40 set aminoplasts can be selected at will; she can Hexamethylohnelamins, such as Pentakis- (methoxy- often a share of up to 80% and more in the methyl> mono- (hydroxymethyl) melamine, hexakis solvent mixture. With relatively non-polar (MethoxymethyQ-melamine or Hexakis- (butoxy- polyesters are also a sole use of these less methyO-melamrä, can be used. polar solvent possible.

However, it is also possible to achieve the miscibility 45 When using polyesters with a high acid number, between the resinous aminoplasts and the polyesters which have a large number of polyesters to be used according to the invention as well as non-esterified carboxyl groups, it is their compatibility when stoving Of course, it is also possible to improve aqueous solutions by preparing the mixture of solutions from. This can be done according to the known and common polyester and aminoplast certain amounts (up to 50 borrowed methods (vgL for example WA SO percent by weight, based on the total amount of giant, »solvent-free paint systems, Curt R. Vin solvents) of high-boiling polar solvents Losem for centz-Verlag, Hanover 1967, p. 432ff.), In which both resins such. B. ÄthylglykoL Äthylglykol- usually the carboxyl groups completely or partially acetate, butylgrycol or cyclohexanone, are added or neutralized with amines and optionally, however, preferably polyester and aminoplast in a known manner, in substance or preferably in solvent, in addition to water-miscible solvents are, which serve as LöscvermitÜer, solution reacts with each other, whereby care must be taken. B. to use aminoplasts borrowed by brief heating; the niedemtölekudes mixture or the common solution of the 60 laren, defined precursors of the aminoplasts are also both resins, optionally in the presence of a catalyst particularly suitable for this purpose, such as. B. organic or mineral The weight ratio of polyester to Ammoplasic acids can be achieved. It is also possible, can vary between 50:50 and 90:10, preferably between 65:35 and 85:15; the optimal resin to amino and / or anüdogruppen contained ratio for the before or during the production of the aminoplast- «5 respective intended use of the lacquers can be easily controlled substances such. B. urea, benzo determine. It should be noted that haufi guanamine or melamine, and aldehydes, such as. B. by increasing the proportion of aminoplast the hard

increases the paint films and reduces their elasticity is, while when the aminoplast content is reduced, the hardness decreases and the flexibility increases.

The total binder content of the paints can vary within the usual limits depending on the intended use. Low-viscosity, linear polyesters containing predominantly hydroxyl groups, ie those with average molecular weights between 250 and about 800, can also be used without solvents in combination with low-molecular, defined precursors of aminoplasts. Such mixtures are applied at room temperature or if desired at temperatures up to 7O ⁰ C (to reduce the processing viscosity) in brushing, rolling or dipping process on the objects to be coated. The thickness of the wet layer should not be too high to avoid the formation of bubbles. It is also possible to further improve the processing properties of such solvent-free coating agents by adding small amounts of solvent (up to about 10 percent by weight, based on the total binder), ie further reducing the viscosity of such systems and suppressing the tendency to form bubbles.

contain substances, for example pigments, leveling agents and additional other binders such as ζ B. epoxy

nfr ^Un _e i? S ^r0Xy T ^lgri l ^PPen ^ ^ltlge _f ^S ^^ arze

The varnish obtained is applied and at

Baked in at temperatures between 100 and 250 ºC.

a ₅

30th

Paint solutions that, as described above, by neutralizing polyols containing carboxyl groups esters with amines are obtained dif Vernei treatment with water-soluble aminoplasts by adding, for example, 0.5% p-toluenesulfonic acid (based on on the total binder)

Also by reacting a low-acid polyester with an anhydride of a relatively strongly acidic dicarboxylic acid, e.g. B. maleic anhydride, ZZ can subsequently increase the acid number of the polyester and, 0 so even without the addition of strong samS. Substances may lower baking temperatures. The acid number of a polyester is usually increased in the melt, for which purpose the SchmeKes ^

resistant. If the coatings a Wärmealterunj of 72 hours at 100 ⁰ C subjected to visible yellowing is sterile determine; a heat aging of 72 hours at 150 ⁰ C, the OF INVENTION to the invention coating as resistant to yellowing of the coatings are resistant to convey opposite solvents such as xylene, benzene, gasoline mixtures, Estonian and ketones. In addition, they have good * acid and alkali resistance. In salt spray attempts, tropical tests and tests in the weatherometer, they show good corrosion protection and weather resistance.

The most outstanding feature of the invention according to the coatings produced, however, their great elasticity and high hardness are

The elongation behavior of coatings is ge comfortably described by the Erichsen cupping test (according to DIN 53 156) and as Mal the deepening of the painted sheet metal for elasticity! indicates in mm at which the lacquer layer begins to tear. It is essential for this test method that the deformation of the coating takes place slowly (feed rate: 0 2 mm / sec)

Di <provides a clue for the behavior of coatings in the event of sudden deformation so-called impact depth measurement. This Messunj can be used, for example, with the impact deepening device 226 / D from Erichsen, Hemer-Sundwig, dirch be guided. In this device, a hemisphere with a radius of 10 mm is covered by a falling; Weight from the back of the paint job in there

As stated at IeAd esSnTund

? λα ⁸ ^ ^es " ^Sta , ⁿ ? l ^{S the T} f
™? fS? ^ calibration tests

withstand ϊ Γη

higher or vl

Approach up to the complete AddMon of the AnSyS heated to temperatures of up to about 150 ° C vfrd. However, there are no difficulties, the dyke reaction in £ solution of the *** ££££%. called reaction conditions thin process; However, care must be taken when doing this! that the solution does not contain any functional groups,
called ReaJctiom ^ eSiige ^
Acid anhydride react köanen.

The upper parts have been manufactured according to the design an abundance of good properties. They are high gloss very easily pigmentable and yellowing

from

_fc

« ₅ ·" ^ch l ^elastic
? ^smd > _Λ ? * ^τ

J ^ ff ^herges ^ ¹ _f ^? ^ α «findongeganaB rest aui

Starting products are obtained '^^^ ^{Λ aUCh} ^

Heavy loads exerted ^ ^{ώβ ljlclaerun} S ™ * »« * «** ~ * ^B

used poly or he

^such

pn verarba-Arbeitsgägen ausgenuo

Polyester production indicating melamine derivative). Table 2 contains the

Test values of the coatings obtained from the following

A mixture of 270 g of butanediol (1,3) (3MoI), comparative examples 1 to 4 described polyesters

186 g of ethylene glycol (3 mol), 146 g of adipic acid (1 mol) were produced, and 592 g of phthalic anhydride (4 mol) is under 5

Stirring and passing through a weak nitrogen stream Comparative Example 1 according to the following time-temperature schedule heated 2 hours at 140 ⁰ C, 2 hours at 160 ^c C, 1580 g of the symmetrical bis (hydroxyethyl) -äthers 4 hours at 180 ⁰ C. , 4 hours at 19O ⁰ C and the bis-phenol-a (5 mol) with 400 g of amber-26 hours at 200 ⁰ C. during this time a total io säureanhydnd (4 moles) while passing a stick 98 g water deposited. The clear, colorless resin stream is ^{heated to 180 °} C. for 6 hours. The remainder has an acid number of 2.5 mg KOH / g and a small amount of water of reaction then results in a hydroxyl number of 66.1 mg KOH / g, which means that a vacuum of about 20 torr away, corresponds to an average molecular weight of 1580. The polyester produced in this way has an acid number of polyester is in a mixture of 6 parts by weight 15 5 mg KOH / g; it is dissolved in a xylene-methylethyl-xylene, 2 parts by weight of butanol and 2 parts by weight of a ketone-cyclohexanone mixture (1: 1: 1) to give a 50pro-ethylglycol acetate to give a 60 percent solution.

Comparative example 2

Manufacture of a lacquer *>

(Example 2 from U.S. Patent 2,460,186)

The solutions of the polyesters in suitable solutions 148 g of phthalic anhydride, 146 g of adipic acid, 278 g

medium, usually a mixture of xylene and a 2-ethylhexanediol (l, 3) and 110 ml of xylene

polar solvent, with a commercially available within 4 hours to 180 ⁰ C and in further

55 percent solution of a melamine-formaldehyde »5 ^{heated to 200 0} C for 4 hours, the formed

Condensate is separated in a xylene-butanol mixture (1: 1) or with water using a water separator,

a commercially available hexamethylolmelamine derivative in the Thereafter is slow within 4.5 hours

desired solids ratio mixed. To a the solvent is distilled off, so that at the end of a

Polyester-melamine resin ratio of 7: 3 is reached einzu- temperature of 24O ⁰ C, place, for example, 117 g of a 60 percent 30

Solution of the polyester with 54.5 g of the above-mentioned comparative example 3 Mixed melamine resin solution; should be polyester and

Melamine-formaldehyde condensate is not compatible with each other (example 1 from Ullmann's Encyclopedia of the tech-compatible, the mixture of the solutions nischen Chemie, 3rd edition, vol. 14, p. 87, Urban & - for low-acid polyesters with the addition of 0, 5% 35 Schwarzenberg, Munich-Berlin, 1963) p-toluenesulfonic acid, based on the total amount of 1400 g of adipic acid (9.6 mol) and 675 g of ethylene polyester and aminoplast - 10 to 60 minutes on glycol (10.9 mol) are heated while passing a 50 to 100 ^{0 C.} Stream of nitrogen was slowly heated to 130 to 14O ⁰ C.

For the production of solvent-free paints, it is achieved that when the

the low-viscosity polyester and a commercially available hexa-water reaction water does not pass over any glycol, becomes a

methylolmelamine derivative in the desired solids part of the distillate as reflux to the column

ratio mixed together. given. Within several hours, the reaction mixture is heated to 200 ⁰ C, then cooled to 150 ⁰ C

Manufacture of a varnish color and the condensation under vacuum continued until

♦ 5 they end at 200 Torr and 200 ⁰ C after 5 to 8 hours.

A clear coat is used to produce a paint color. The waxy polyester has a hydroxyl

in a binder-pigment ratio of 2: 1 with a TiO ₂ number of 54 mg KOH / g and an average molecular

pigmented. weight of 2000; he is in a xylene methyl

ethyl ketone mixture (1: 1) to a 50prozentigei

Production and testing of the coatings 50 solution dissolved.

The clear lacquer or the lacquer color comparative example 4 is used for testing

applied to test panels and glass plates and baked to lower the baking temperature (Example 2 from Ullmann's Encyclopadie der tech is lacquers that were produced using polyesters 55 nischen Chemie, 3rd edition., Vol. 14, p. 87, Urban i low acid number , 0.5% p-toluene-Schwarzenberg, Munich-Berlin, 1963) sulfonic acid (based on the total binder) 316 g adipic acid (2.16 mol), 480 g phthalic acid

The layer thickness of the joints on which the anhydride (3.24 mol) and 374 g of ethylene glycol (6.5 Mo! test is carried out) is 40 to 60 μ in all examples, while a stream of nitrogen is passed over it. The hardness test is carried out in accordance with DIN 53157 , heated for 60 sam at 160 to 200 ⁰ C, are passed above loading to USg distillate · when the examination of the elasticity after the. it has to be ensured that di overridden methods. transition temperature at the top of the column 100 ° '

Examples 1 to 14 are not exceeded in Table 1, and are then compiled in ascending order, the type of vacuum used also being given in 6 hours, 19 g of di-melamine resin distilled off. (In the column "Type" 5 polyester has an acid number of 3 to 4 mg KOH _{1 of} the melamine resin "K means that a butylated and a hydroxyl number of 56 mg KOH / g; it is used in melamine-formaldehyde condensate, a Xylene-methylethylketone-cyclohexanone-G during HMM the use of a Hexamethylcl- mix (1: 1: 1) dissolved to a 50 percent solution

Table 1

polyester
out Mitt
leres
mole
kular
Weight Weight
ratio
polyester
to melamine
resin to TiO, i Type of
melamine
resins Kataly
sator Burn-in
conditional
worked hardness
after
DIN
53 156 Deep- Impact
deep at
game
No. [Mole] [sec] pulling
capable-
speed
after
DIN
53 156 [mm] 4 BG (*)
2 ÄG (*)
4PSA (*)
1 BSA (*) 1890 70: 30: 0
80: 20: 0
80:20:50
80: 20: 0
80:20:50 HMM (*)
HMM
HMM
HMM
KH 0.5% pTS *)
0.5% pTS
0.5% pTS
0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 '
140 ° 30 '
160 ° 30 '
140 ° 30 ' 195
158
130
185
116 [mm] > 5
> 5
5
4 to 5
4th 1 3BG
3 AG
4PSA
IASH 1580 70: 30: 0
70:30:50 HMM
HMM 0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 ' 137
109 10.5
11.9
11.3
10.5
10.4 > 5
> 5 2 IBG
IAG
0.6 PSA
0.4AS
solvent free 285 70: 30: 0
70:30:50
70: 30: 0 HMM
HMM
HMM 0.5% pTS
0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 '
160 ° 30 ' 100
106
102 9.0
8.9 > 5
4 to 5
2 to 3 3 4BG
2 AG
3.5 IPS (*)
1.5AS 1540 70: 30: 0
70:30:50 HMM
HMM 0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 ' 134
110 7.8
6.7
6.8 > 5
> 5 4th 1.3BG
0.7 AG
0.6 PSA
0.4AS
solvent free 310 70: 30: 0
70:30:50 HMM
HMM 0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 ' 118
105 9.7
9.7 > 5
4th 5
If 2BG
2 AG
2.1 PSA
0.9AS
solvent free 70: 30: 0 HMM 0.5% pTS 160 ° 30 ' 132 8.0
7.8 3 3BG
2 AG
3PSA
IAS 750 70: 30: 0
70:30:50
70: 30: 0 HMM
HMM
HMM 0.5% pTS
0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 '
160 ° 30 ' 132
112
127 .6.9 > 5
> 5
3 6th 5BG
5 AG
7.5 PPE
1.5AS 920 70: 30: 0
70:30:50 HMM
HMM 0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 ' 148
128 8.7
8.6
7.2 > 5
> 5 7th 5BG
3 AG
6PSA
IBSA 1980 70: 30: 0
70:30:50 HMM
HMM 0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 ' 119
106 9.2
9.0 > 5
5 8th 6BG
4 AG
8PSA
IBSA 1620 70: 30: 0
70:30:50 HMM
HMM 0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 ' 167
136 10.3
10.0 > 5
5 9 3BG
3 PGH
4PSA
IAS 1960 70: 30: 0
70:30:50 HMM
HMM 0.5% pTS
0.5% pTS 140 ° 30 '
140-30 ' 144
126 8.3
7.9 > 5
5 10 5BG
5PG
7 pc a 1360 70: 30: 0
70:30:50 HMM
HMM 0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 ' 152
122 9.7
9.5 5
5 11th / Γόη
2AS 1930 70: 30: 0
70:30:50 HMM
HMM 0.5% pTS
0.5% pTS 140 " 30 '
140 ° 30 ' 122
118 8.8
7.6 5
4th 12th 9.4
M:

15th

Table 1 (continued)

May be
game
No. polyester
out
(MoI] Mitt
leres
mole
kular
Weight Weight
ratio
polyester
to melamine
resin to TiO, Type of
MeI-
amine
harzcs Kataly
sator Burn-in
conditions hardness
after
DIN
53156
[sec] Deep-
pulling
capable-
speed
after
DlN
53156
[well] Impact
deepening
[mm] 13th
14th
15 (**) 4BG
2PG
4PSA
IAS
2BG
2 AG
2PSA
IBSA
3BG
2 AG
4PSA
IAS 1320
710
975 70: 30: 0
70: 30: 0
70: 30: 0
70:30:50
80: 20: 0
80: 20: 0 HMM
HMM
HMM
HMM
HMM
HMM 0.5% pTS
0.5% pTS
0.5% pTS
0.5% pTS
0.5% pTS 140 ° 30 '
140 ° 30 '
140 ° 30 '
140 ° 30 '
160 ° 30 '
180 ° 30 ' 142
120
149
137
200
183 9.9
9.0
8.3
7.9
> 10
> 10 5
5
4th
3 to 4
> 5
> 5

) Abbreviations:

BG = butanediol- (1.3) AG = ethylene glycol PSA = phthalic anhydride BSA = succinic anhydride HMM = hexamethylol melamine derivative

pTS = p-toluenesulfonic acid

K = melamine-formaldehyde condensate AS = adipic acid IPS = isophthalic acid PG = propanediol- (1,2)

**) This example concerns a water-soluble clear lacquer which was obtained as follows:

The polyester with an acid number of 49.7 mg KOH / g and a hydroxyl number of 62.5 mg KOH / g is ^{diluted with isopropanol at a temperature between 80 to 1} M ⁰ C to form a 77% solution and after cooling at room temperature neutralized with the equivalent amount of Triäthyla.min. The mixture is adjusted to a solids content of 50 percent by weight with water. A commercially available hexamethyrolamine amine derivative is then mixed in, a polyester / aminiplast ratio of 8: 2 being achieved. It is then diluted again with water to a solids content of 50 percent by weight.

Table 2

Ver
equal
at
game
No. Polyester
[Mole] Mitt
leres
Mole
Weight Weight
ratio
polyester
to melamine
resin to TiO, Art Isa
Melamine-
resin Kataly
sator Burn-in
conditions hardness
after
DIN
53 157
[secl Deep-
pulling
capable-
speed
after
DIN
53156
[mm] Impact
deepening
[mm] 1
2
3
4th 5 HÄBA *)
4BSA
1.91 ÄHD »)
1 PPE *)
1 ADS *)
10.9 AG *)
9.6 ADS
6.5 AG
3.24 PSA
2.16 ADS 1880
1750
.2000
2050 70: 30: 0
70: 30: 0
70: 30: 0
70: 30: 0
70:30:50
70: 30: 0
70:30:50
70: 30: 0 K. *)
HMM *)
K
HMM
K.
HMM
K
HMM 0.5% pTS
0.5% pTS
0.5% pTS
0.5% pTS
0.5% pTS
0.5% pTS
0.5% pTS
0.5% pTS 130 ° 30 '
130 ° 30 '
130 ° 30 '
130 ° 30 '
130 ° 30 '
130 ° 30 '
130 ° 30 '
130 ° 30 ' 135
126
35
19th
45
39
25th
22nd 1.1
1.9
2.0
> 10
6.1
8.8
7.9
9.1 <1
<1
<1
> 5
> 5
> 5
> 5
> 5

*) Abbreviations:

HÄBA = bis (hydroxyethyl) ether of bisphenol A BSA = succinic anhydride

K = melaraine-formaldehyde condensate HMM = hexamethylolmelamine derivative

AHD = 2-ethyl-hexanedioKU) PSA = phthalic anhydride AS = adipic acid AO = ethylene glycol

609 652/120

Claims (1)

Patent claims: L Liquid coating agent based on a mixture of binder and organic solvents or water and the binder water-solubilizing additives or optionally also on a solvent-free basis, as a binder A. 50 to 10 weight percent aminoplasts and /. or their low molecular weight defined precursors and 15th B. 50 to 90 percent by weight of hydroxyl-containing and carboxyl-containing polyesters from aliphatic diols and optionally other diols on the one hand and aromatic ones and aliphatic dicarboxylic acids, on the other hand, in addition to optionally customary additives contain, the binder also by mixed condensation of aminoplasts and / or their low molecular weight precursors with the polyesters or by co-condensation of the Starting products of the aminoplast production may have been made with polyesters, characterized in that linear Polyesters with average molecular weights between 250 and 2500 are used, which are produced by esterification Mixtures 1 and II have been prepared, Mixture I from component IÄ and up to 50 to 30 mole percent ¹ from component; L2 exists, 3 Coating agents according to Claims 1 and 2, characterized in that predominantly hydroxyl groups containing linear polyesters with average molecular weights between 250 and 800 in combination with low molecular weight, defined precursors of aminoplasts in solvent-free or low-solvent form can be used. 4. Coating agent according to claim 3, characterized in that the coating agent up to 10 percent by weight of solvent, based on the total binder. 5. Coating agent according to claim 1 to 4, characterized in that linear polyester with Average molecular weights between 700 and 2000 are used, for their production as Component 11.2 succinic anhydride has been used.