DE1805192C3 - Coating agents - Google Patents

Description

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 linear polyesters Propanediol (1,2) and optionally other diols on the one hand and aromatic and aliphatic ones Dicarboxylic acids on the other hand

optionally contain in addition to customary additives and auxiliaries, the binder also by co-condensation of aminoplasts and / or their low molecular weight defined precursors with the polyesters or produced by co-condensation of the starting products of the aminoplast production with the polyesters may have been.

From DT-PS 10 15 165 it is 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 Manufacture coatings. The paint films obtained have a low chemical resistance on.

It is also known from this publication that one can use extremely chemically resistant coatings obtained when an alkylated melamine-formaldehyde or urea-formaldehyde condensation product combined with a linear polyester obtained by polyesterification of a dicarboxylic acid with a Diol of the general formula

is obtained in which A is a 2-alkylidene radical having 3 to 4 carbon atoms, R is an alkylene radical having 2 to 3 carbon atoms, m and η are each at least 1 and the sum of m and η is not greater than 3. The coatings obtained in this way are hard, but very brittle (see Comparative Example 1).

In US-PS 24 60 186 polyesters from 2-ethyl-hexanediol (l, 3) as a plasticizer are exceptional Value for use in urea-formaldehyde or melamine-formaldehyde condensation products described. The coatings obtained according to this information are in part stretchable and impact-resistant, but too soft (see Comparative Example 2).

In addition, our own experiments show in which mixtures of linear polyesters and a melamine-formaldehyde resin were cured so that the coatings obtained are stretchable, but soft (see Comparative Examples 3 and 4).

The production is from Houben-Weyl, Methods of Organic Chemistry (Vol. 14/2, pp. 21, 22, 24 and 29) linear mixed polyester known. In addition, it is stated that these polyesters include i.a. with aminoplasts can be networked. An indication that these products can be processed into paint raw materials, is missing. In the same publication (p. 337/338) it is shown that aminoplasts are made with polyesters

/ Vdipic acid / polyol or with unsaturated compounds, such as monoglycerides of native fatty acids can be plasticized. The last mentioned Reaction products should also be used as coating agents. An indication of linear Polyester - especially those of a certain composition - To be used in connection with aminoplasts as a coating agent, is used in this publication not given.

From US-PS 28 01 189, 29 31 739 and 32 07 623 are ic linear polyesters known, which, however, are not used in combination with aminoplasts. you will be applied as such to glass fibers and should serve as an adhesion promoter if the glass fibers are used as reinforcement material, e.g. for unsaturated polyester resins.

US-PS 33 92 135 describes the use of linear polyesters as plasticizers in crosslinked Polyvinyl halide resins. Nowhere in the pamphlet can it be inferred that this is here listed polyesters in connection with aminoplasts result in excellent coating agents.

The invention is based on the object of producing coatings in which high elasticity with great Unite hardness.

This object has been achieved, surprisingly, in that coating agents have been found in which as Component B linear polyesters with average molecular weights between 600 and 3000 are used have been prepared by esterification of mixtures I and Ii, mixture I

1.1 to 70 to 30 mol percent, preferably 60 to 40 mol percent, from propanediol (1,2) and

1.2 to 30 to 70 mol percent, preferably 40 to 60 Mole percent, composed of dipropylene glycol,

and optionally up to 30 mole percent, preferably up to 20 mole percent, of the total amount of the Components 1.1 and 1.2 by one or more others aliphatic or cycloaliphatic diols in which the hydroxyl functions by 2 to 8 Carbon atoms are separated and optionally instead of up to 2 of the carbon atoms, oxygen atoms can stand, which in turn should be separated from one another by at least 2 carbon atoms, and Mixture II

11.1 from 100 to 50 mole percent, preferably from 95 to 70 Mole percent, from one or more aromatic or cycloaliphatic dicarboxylic acids and / or their derivatives and

11.2 from 0 to 50 mol percent, preferably from 5 to 30 mol percent, of one or more aliphatic Dicarboxylic acids with 4 to 12 carbon atoms and / or their derivatives.

As diols to be used in minor amounts, in which the hydroxyl functions are replaced by 2 to 8 Carbon atoms are separated and optionally up to 2 of the carbon atoms by oxygen atoms can be replaced, which in turn should be separated from one another by at least 2 carbon atoms, are suitable e.g. B.

65

Ethylene glycol, propanediol (1,3), butanediol (1,2).
Butanediol (2,3), butanediol (1,3), butanediol (1,4),
2,2-dimethyl-propanediol- (1,3), hexanediol- (1,6),

2-ethyl-hexanediol- (1,3), cyclohexanediol- (1,2),
Cyclohexanediol (1,4),

1,2-bis (hydroxymethyl) cyclohexane,

1,3 bis (hydroxy methy l) cyclohexane,

1,4-bis (hydroxymethyl) cyclohexane,

x, 8-bis (hydroxymethyl) -tricyclo- [5.2, l, 0 ^2fl ] -decane,

where χ stands for 3, 4 or 5, diethylene glycol, triethylene glycol or tripropylene glycol. Cycloaliphatic diols can be used in their cis or trans form or as a mixture of both forms.

Aromatic or cycloaliphatic dicarboxylic acids are, for. B.

Phthalic acid, isophthalic acid,

Hexahydroterephthalic acid,

Tetrahydrophthalic acid, hexahydiophthalic acid,

Hexahydroisophthalic acid and endomethylene

or endoethylene-tetrahydrophthalic acid,

Hexachloroendomethylene tetrahydrophthalic acid or tetrabromophthalic acid

suitable, the cycloaliphatic dicarboxylic acids in their trans or cis form or as a mixture of both Shapes can be used. The use of dicarboxylic acids, in which the carboxyl groups in 1,2-position are arranged, in particular of phthalic acid and hexahydrophthalic acid is preferred.

Succinic acid, glutaric acid, adipic acid, suberic acid are particularly suitable as aliphatic dicarboxylic acids, Sebacic acid, decanedicarboxylic acid or 2,2,4-trimethyladipic acid. The use of aliphatic dicarboxylic acids with 4 to 6 carbon atoms, especially adipic acid, is preferred.

Instead of the free dicarboxylic acids, their esters with short-chain alkanols, e.g. B. dimethyl, Diethyl or dipropyl esters can be used. If the dicarboxylic acids form anhydrides, they can also these are used, e.g. B.

Phthalic anhydride,
Hexahydrophthalic anhydride,
Tetrahydrophthalic anhydride,
Succinic anhydride or glutaric anhydride.

Coatings with particularly good properties are obtained when using polyesters with medium Molecular weights from 800 to 2500, in particular from 1000 to 2000, which predominantly contain hydroxyl groups, d. H. have been prepared with a molar excess of diols.

The polyesters can be prepared by all known and customary processes, with or without a catalyst, with or without passing through a stream of inert gas, as solution condensation, melt condensation or azeotropic conversion, at temperatures of up to 250 ° C. or higher, with the released water or the liberated alkanols are continuously removed. The esterification is almost quantitative and can be followed by determining the hydroxyl and acid numbers. As a rule, the esterification conditions are chosen so that the reaction is as complete as possible, ie until the acid number in the case of polyester batches is from η Mo! Diol and (n ~ \) mol of dicarboxylic acid is less than 7 mg KOH / g. In the case of approaches from η Moi Dioi and (n + \) Γνίοΐ dicarboxylic acid, esterification is carried out until the hydroxyl number is below 7 mg KOH / g. The molecular weight

of the polyester can be regulated in a simple manner via the use ratio of diol and dicarboxylic acid.

The esterification temperature is chosen so that the Loss of volatile substances remains low, d. i.e., at least during the first period of esterification, esterification is carried out at a temperature which is below the boiling point of the lowest-boiling starting substance.

When producing the polyester it should be noted that ι ο Both the molecular weight of the polyester and its composition influence the properties of the have lacquer films made from them. In the case of higher average molecular weights, the hardness of the Lacquer film decreases while the elasticity increases, on the other hand leaves the flexibility at lower molecular weights of the paint film with a simultaneous increase in hardness. Differences also have a similar effect in the composition of the polyester from: With a higher proportion of aliphatic dicarboxylic acids and with a larger chain length of the aliphatic dicarboxylic acids, the elasticity of the paint film increases, while its hardness is reduced. The opposite is the case with an increasing proportion of aromatic and / or cycloaliphatic Dicarboxylic acids in polyester make the paint film harder and less flexible. A similar influence exercise the diols: With increasing chain length of the open-chain diols and with increasing proportion These diols in the polyester make the paint film softer and more flexible, while using diols with short and branched carbon chains or with cycloaliphatic rings for the production of the polyester the lacquer films produced from these polyesters in the As a rule, the higher the proportion of these diols, they become harder and less elastic. Knowing this It is possible to regulate without difficulty, within the scope of the claimed range, using polyester for the respective intended use to select optimal properties and for the invention Use coating agents.

The known reaction products of aldehydes, in particular, are suitable aminoplasts Formaldehyde, with several amino or amido-bearing substances in question, such as. B. with Melamine, urea, dicyandiamide and benzoguanamine. Those modified with alcohols are particularly suitable Aminoplasts.

Because of the sometimes only limited compatibility of these resinous products with those according to the invention Polyesters to be used are preferably the low molecular weight, defined precursors of aminoplasts, which are practically unlimitedly miscible with the polyesters to be used according to the invention are used. Such defined precursors of aminoplasts are e.g. B. tetramethylol benzoguanamine, trimethylol melamine or hexamethylolmelamine, which can also be used in partially or completely etherified form, e.g. B. as Tetrakis (methoxymethyl) benzoguanamine, tetrakis (ethoxymethyl) benzoguanamine or polyethers of hexamethylolmelamine, such as hexamethoxymethylmelamine or hexabutoxymethylmelamine, can be used be able.

However, it is also possible to improve the miscibility between the resinous aminoplasts and the polyesters to be used according to the invention, as well as their compatibility during stoving, by adding certain amounts (up to 50 percent by weight, based on the total amount) to the mixture of the solutions of polyester and aminoplast Solvent) to high-boiling polar solvents for both resins, such as. B. ethylglycol, ethylglycol acetate, butylglycol or cyclohexanone is added or, preferably, polyester and aminoplast are reacted in a known manner in bulk or preferably in solution, whereby care must be taken that the reaction does not progress to crosslinking. Diet, 7 .. B. by briefly heating the mixture or the common solution of the two resins, optionally in the presence of a catalyst, such as. B. organic or mineral acids can be accomplished. It is also possible to use the polyester to be used according to the invention before or during the preparation of the aminoplast resins from z. B. urea, benzoguanamine or melamine and aldehydes to be added to the batch, whereby it is of course also possible to use additional customary alcohols for modifying the plati / ized amino resins thus formed. The methods for producing such plasticized amine-aldehyde resins both for solvent-based and for aqueous paint systems are known.

A large number of commercially available polyesters are available for combination with the polyesters used according to the invention Aminoplasts or their defined precursors are available.

To produce the coatings, polyester and aminoplast or its defined preliminary stages in common paint solvents such as propanol, iso-propanol, butanol, ethyl acetate, Butyl acetate, ethyl glycol, ethyl glycol acetate, butyl glycol, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone, trichlorethylene or mixtures of various such solvents, dissolved. It is of course also possible and recommended for economic reasons, more or less large amounts of less polar solvents, such as. B. benzene, toluene, xylene or higher-boiling aromatic cuts, to be used. The amount of these less polar solvents used is within limits the solubility of the polyesters used according to the invention and their compatibility with. the used Aminoplasts freely selectable; it can often have a proportion of up to 80% and more in the solvent mixture reach.

When using polyesters with a high acid number, i. H. in the case of polyesters, which do not have a larger number have esterified carboxyl groups, it is of course also possible to prepare aqueous solutions. This can be done by the known and customary methods, the carboxyl groups as a rule be completely or partially neutralized with amines and optionally additionally with water Miscible solvents are used, which serve as solubilizers. Of course it is with the Preparation of aqueous paint solutions required to use water-soluble aminoplasts; the Defined precursors of the aminoplasts are also particularly suitable for this purpose.

The weight ratio of polyester to aminoplast can vary between 50:50 and 90:10, preferably between 65:35 and 85:15; that for the The optimal ratio for the respective purpose of use of the paints can easily be determined by a few preliminary tests determine. It should be taken into account that the hardness of the Lacquer films are increased and their elasticity is reduced, while when the aminoplast content is reduced, the

Hardness decreases and flexibility increases.

The total binder content of the paints can vary within the usual limits depending on the intended use.

The paints can contain the usual additives and auxiliaries, for example pigments, leveling agents and additional other binders, such as. B. epoxy resins and silicone resins containing hydroxyl groups.

The lacquer obtained is applied and ^{baked at temperatures between 100 and 250 °} C., ι ο The crosslinking reactions that take place are catalytically accelerated by acids. When using polyesters with a very low acid number, acidic substances can therefore be added to the paint. When adding, for example, 0.5% p-toluenesulfonic acid (based on the total binder), the crosslinking is greatly accelerated. By adding larger amounts of acid, coatings that dry even at room temperature can be produced.

Even by reacting a low-acid polyester with about 1 to 5% of an anhydride, a relatively strong one acidic dicarboxylic acid, e.g. B. maleic anhydride, you can increase the acid number of the polyester later and thus lower the stoving temperatures even without the addition of strongly acidic substances.

The coatings produced according to the invention have an abundance of good properties. They are high-gloss, very easy to pigment and have excellent resistance to yellowing. If the coatings are subjected to heat aging for 72 hours at 100 ^° C., no visible yellowing can be detected; a heat aging of 72 hours at 15O ⁰ C comprises coatings of the invention than resistant to yellowing. The coatings are resistant to solvents such as xylene, gasoline-benzene mixtures, esters and ketones. In addition, they have good acid and alkali resistance. In salt spray tests, tropical tests and tests in the weatherometer, they show an excellent corrosion protection effect and weather resistance.

The most outstanding property of the coatings produced according to the invention, however, is their greatness Elasticity with high hardness.

The elongation behavior of coatings is usually described by taking the Erichsen cupping test (according to DlN 53 156) and as a measure of the extensibility the deepening of the painted sheet metal in mm indicates at which the paint layer begins to crack. It is essential for this test procedure that the Deformation of the coating takes place slowly (feed: 0.2 mm / sec).

A clue for the deterioration of coatings in the event of sudden deformation is provided by so-called impact measurement. This measurement can be carried out, for example, with the impact testing device 226 / D made by Erichsen, Hemcr-Sunclwig. This device has a hemisphere a radius of 10 mm due to a falling weight from the back of the paint into the sheet metal depressed. By changing the height of fall of the fco The depth can be varied by weight. The indentation value (in mm) is given at which the The paint layer begins to tear. (The values given in the examples were obtained in this way, In some examples the value> 5mm is given, since the device described does not have the 1 mm thick deep-plate sheets that are usually used for testing srößcrc cupping allows.)

As stated in the description of the state of the art and proven by comparative tests is, coatings made of linear polyesters and aminoplasts are already known, which are stretchable and also one Withstand impact stress. However, these coatings have a very low hardness (according to DIN 53 157). On the other hand, coatings of high hardness are known, but they are not elastic. In contrast, the coatings obtained according to the invention have both high elasticity and great hardness.

This property profile opens up a wide range of uses for the coatings. In addition to painting Individual parts that are exposed to impact stress come mainly from the painting of materials into consideration, the retrospectively - z. B. by punching - be deformed.

The polyesters used in accordance with the invention give low viscosity solutions. Leave it therefore paints with high solids content can be processed, which saves work steps can be exploited.

Polyester production

A mixture of 103.9 g of propanediol (1,2) (1.37 mol), 134 g of dipropylene glycol (1 mol), 197.3 g of phthalic anhydride (1.33 mol), 33.3 g of succinic anhydride (0.33 mol) and 48.7 g of adipic acid (0.33 moles) was added with stirring and passing a gentle stream of nitrogen is heated according to the following time-temperature schedule: 2 hours at 14O ⁰ C, 2 hours at 160 ⁰ C, 4 hours at 180 ⁰ C, 4 hours at 190 ^° C. and 22 hours at 200 ^° C. During this time, a total of 36 g of water are separated out. The mixture is then stirred for a further 15 minutes at 200 ^° C. and a vacuum of 20 torr. The clear, almost colorless resin has an acid number of 4.0 mg KOH / g and a hydroxyl number of 68.3 mg KOH / g, which corresponds to an average molecular weight of 1,550. The polyester is dissolved in xylene to form a 60 percent solution.

Increasing the acid number of a polyester

1.2% maleic anhydride (based on the pure polyester) is added to the melt of a polyester with a low acid number. After the added anhydride has completely dissolved, the mixture is ^{heated to 120 11} C for 1 hour, as a result of which the acid number of the polyester is increased by 8.56 mg KOH / g.

The acid number of a polyester is usually increased in the melt, jcdocl there is no difficulty in getting the same response ii the solution of the polyester among those mentioned To carry out reaction events; it is dub However, care must be taken that the solvent does not contain any functional groups that fall under the above! Reaction conditions also with the SlUircanhy dritl can react.

Manufacture of a lacquer

The solutions of the polyester in suitable solution; medium, usually a mixture of xylene and egg

10

5 mg KOH / g; it is in a xylene-methylethylketone-cyclohexanone mixture (1: 1: I) to a 50 percent Solution solved.

Comparative example 2

polar solvent, come with a commercially available one

55 percent solution of a melamine-formaldehyde

Condensates in a xylene-butanol mixture (1: 1) or with

a commercially available hexamethylolmelamine derivative im

desired solids ratio mixed. To a

Set a polyester-to-melamine resin ratio of 7: 3, for example, 117 g of a 60 percent

gene solution of the polyester with 54.5 g of said

Mixed melamine resin solution; should be polyester and

Melamine-formaldehyde condensate not ok with each other (example 2 from the USA patent 24 60 186)

be compatible, the mixture of solutions -

for non-acidic polyesters with an addition of 0.5%

p-Toluenesulfonic acid, based on the total amount of 148 g of phthalic anhydride, 146 g of adipic acid, 278 g

Polyester and aminoplast - 10 to 60 minutes on 50 2-ethylhexanediol- (1, 3) and 110 ml xylene are irin-

heated to 100 ° C. '5 half from 4 hours to 180 ° C and in a further 4 hours

heated to 200 ° C, the water formed over
a water separator is separated. After that, will
slowly the solvent within 4.5 hours
distilled off, so that at the end a temperature of

Production of a paint color ^{20 240} ° ^{C is reached}

To produce a lacquer color, a clear lacquer is pigmented _{with TiO 2} in a binder-to-pigment ratio of 2: 1.

Manufacture and testing of coatings

For testing, the clear lacquer or the lacquer color is applied to test panels and glass plates and baked. To lower the stoving temperature, lacquer solutions made using polyesters low acid number, 0.5% p-toluenesulfonic acid (based on the total binder) added. The layer thickness of the films on which the The test is carried out, amounts to 40 to 60 μ in all examples. The hardness test is carried out in accordance with DIN 53157, the Test of elasticity according to the methods described above.

Examples 1 to 9 are listed in Table 1, including the type of used Melamine resin is specified. (In the column "Type of M-iaminharzes" K means that a butylated Mclamine formaldehyde condensation was used, while UMM uses a methylol melamine crival Table 2 contains the test values of the coatings, which are derived from the in the following Comparative examples 1 to 4 described polyesters were prepared.

Comparative example 3

(Example 1 from Ullmann's Encyclopedia of
technical chemistry, 3rd edition, volume 14, page 87,
Urban & Schwarzenberg, Munich-Berlin, 1963)

1400 g of adipic acid (9.6 mol) of ethylene glycol and 675 g (10.9 moles) are heated while passing a stream of nitrogen slowly to 130 ⁰ C to 140 ⁰ C. In order to ensure that no glycol passes over when the water of reaction is distilled off, part of the distillate is fed to the column as reflux. Within several hours the reaction mixture at 200 ⁰ C is then heated to 15O ⁰ C cooled and the condensation untei

Vacuum continued until it is completed at 200 Torr and 200 ⁰ C Nasr 5 to 8 hours. The waxy polyester has a hydroxyl number of 54 mg KOH / g and an average molecular weight of 2000; it is dissolved in a xylene-methyl ethyl ketone mixture (1: 1) to form a 50 percent solution.

Comparative example 4

(Example 2 from Ullmann's EncyclopUdic der
technical chemistry, 3rd edition, volume 14, page 87,
Urban & Schwarzenberg, Munich-Berlin, 19bJ)

Comparative example

HBOg of the symmetrical bis- (hydroxyethyl) -ilhcrs ties bisphenol-A ( ^r ) mol) are heated with 400 g of succleic acid anhydride (4 mol) under passage of a slicklol-oil for hours at 180 ° C. Remaining amounts of turning water are then by application A vacuum of about 20 torr. The polyester produced in this way has a content of 316 g of adipic acid (2.16 mol), 480 g of phthalic acid (3.24 mol) and 374 g of ethylene glycol (6.5 Mc are passed over of a Sticksloffstromcs lani

Heated to 160 to 200 "C until 118 g of still have passed over. Care must be taken here that the transition temperature at the top of the column does not exceed 100". Then a further 19 g are distilled off in 6 hours with increasing vacuum. Ό

h _S polyester has an acid number of 3 to 4 mg KOH / gw a hydroxyl number of 5 mg KOH / g; he will be in a

Xylene-methylethylketone-cyclohexanone-Ciemiscli
(1: 1: I) to a dissolved ^r) Oprozentigcn solution.

11th

Table 1

at Polyester Middle Weight reduction Type of catalyst Burn-in hardness Deep drawing Impact game Mole ratio poly Melamine- condition after capability running No. Weight ester to MeI- resin gene DIN according to DlN amine resin too 53 157 53 156 (Mole) TiO2 (sec) (mm) (mm)

4 PG *) 4 DPG *)

6 PSA *) 1 ADS *)

! 3PG 3DPG 4PSA 1 ADS

! 4 PG 3DPG 4.8 PSA 1.2 ADS

\ 2 PG 3DPG

3.2 PSA 0.8 ADS

5PG 4 DPG

7 PPE

1 ADS

2 PG 2DPG

2.3 PSA 0.7 ADS

4 PG 3DPG 1 AG *) 6PSA 1 ADS

4PG 3DPG 1 CHDM ·) 6PSA 1 ADS

4 PG 3DPG ί PSA 1 BSA *) I ADS

) Abbreviations: PC.
DPG
PPE
ADS
HMM

ps

MA

1750 70: 30: 0 70: 30: 80: 20: 80: 20:

1300 70: 30: 0 70: 30: 80: 20: 0

1500

1980

840

1710

1800

1550

70:30: 70: 30:

1080 70: 30: 0 70: 30: 50 80: 20: 0

70: 30: 70: 30: 80: 20:

70: 30: 80: 20:

70: 30: 0 70: 30: 80: 20:

70: 30: 0 70: 30: 80: 20: 50

70: 30: 70: 30:

Propaiuliol- (1,2) - Dipropylene Glycol »Phlhalsliurcanhydrid» Adipinsllurc

"Hxamethylolniclamiiulcrival " p-Toliiolsulfonsaure "· Melamine-formaldehyde condensate

Maleic anhydride

(D ll'Pl

HMM *)
HMM
HMM
K *)

HMM
HMM
K.

HMM
HMM

HMM
HMM
HMM

HMM
HMM
HMM

HMM
HMM

HMM
HMM
HMM

HMM
HMM
HMM

HMM

HMM

0.5% pTS *) 0.5% pTS 0.5% pTS 0.5% pTS

0.5% pTS 0.5% pTS 1.2% MA *)

0.5% pTS 0.5% pTS

0.5% pTS 0.5% pTS 0.5% pTS

0.5% pTS 0.5% pTS 0.5% pTS

0.5% pTS 0.5% pTS

0.5% pTS 0.5% pTS 0.5% pTS

0.5% pTS 0.5% pTS 0.5% pTS

0.5% pTS 0.5% pTS

150 ° / 30 '
150 ° / 30 '
150 ° / 30 '
150 ° / 30 '

150 ° / 30 '
150 ^l 730 '
150 "/ 30 '

150 ° / 30 '
150 ° / 30 '

150 ° / 30 '
150 ° / 30 '

150 ° / 30 '
150 ° / 30 '
150 ° / 30 '

150 ° / 30 '
150 ° / 30 '
150 ° / 30 '

I5O'73O '
150'730 '

142 165 137 151

151 168 156

148 153

150 ° / 30 '128 150 ° / 30' 137 150 ° / 30 '118

150 ° / 30 '132 150 ° / 30' 149 150 ° / 30 '141

156 164

153 166 148

156 170 154

118 IJ6

9.1 8.2> 1 9.4

9.1 8.6

8.8

9.8

8.8

9.4 7.8

8.6 9.3

8.1 8.8

8.8

5 4

> 5 4

> 5 5

> 5

4-5

> 5

> 5

> 5

4-5> 5

4 2-3

> 5

4-5

> 5

4 4-5

> 5 4-5

AG

CMI) M
ns Λ

Maleic anhydride

(The sllurcnrmc'Polyester is (lurch Ucaklion with the specified amount of maleic anhydride

the pure polyester - brought to a ^{higher level according to ik'i 1} described Mcllioilc.)

Ähllkl

Z M- ¹ »is ⁿ (fiy ^y (iwxy"'* - iiiyl) a ^ i <' ^llL '' ^llin

- Hcrnsleic acid anhydride

Table 2

Ver Polyester Mitt Weight Type of Kata Burn-in hardness Deep drawing Schli equal leres ratio Melamine- lyser conditional after capability deeply example Mole Polyester too resin worked DIN after No. Weight Melamine resin 53 157 DlN to T1O2 53 156 (Mole) (sec) (mm) (mm]

5 HÄBA *)
4 BSA *)

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: 70: 30: 0

70: 30: 70: 30: 0

K *) HMM *)

HMM

K HMM

HMM

0.5% pTS 130 ° / 30 '135 1.1 <1

0.5% pTS 130 ° / 30 '126 1.9 <1

0.5% pTS 130 ° / 30 '35 2.0 <1

0.5% pTS 130 ° / 30 '19> 10> 5

0.5% pTS 130 ° / 30 '45 6.1> 5

0.5% pTS 130- / 30 '39 8.8> 5

0.5% pTS 130 ° / 30 '25 7.9 > 5

0.5% pTS 130 ° / 30 '22 9.1> 5

*) Abbreviations:

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

Melamine-formaldehyde condensate Hexamethylolmelamine derivative

2-ethyl-hexanediol- (1,3)

Phthalic anhydride adipic acid

Ethylene glycol

Claims (3)

Patent claims: 1. Liquid coating agents based on a mixture of binding agents and organic ones Solvents or water and the binder solubilizing additives or optionally on solvent-free base that acts as a binder A. 50 to 10 percent by weight aminoplasts and / or their low molecular weight defined Pre-stages and B. 50 to 90 percent by weight hydroxyl-containing and carboxyl-containing linear Polyesters from propanediol (1,2) and optionally other diols on the one hand and aromatic ones and aliphatic dicarboxylic acids on the other hand optionally in addition to the usual additives and auxiliaries contain, the binder also by co-condensation of aminoplasts and / or their low molecular weight defined precursors with the polyesters or by co-condensation of the Starting products of the aminoplast production can have been made with the polyesters, characterized in that polyester with average molecular weights between 600 and 3000 are used, which have been prepared by esterification of the mixtures I and II, wherein Mixture 1 1.1 to 70 to 30 mol percent from propanediol- (1,2) and 1.2 consists of 30 to 70 mol percent dipropylene glycol, ^ ⁵ and optionally up to 30 mol percent of the total amount of components 1.1 and 1.2 can be replaced by one or more other aliphatic or cycloaliphatic diols, in which the hydroxyl functions are separated by 2 to 8 carbon atoms and optionally instead of up to 2 of the carbon atoms can be oxygen atoms, which in turn are represented by at least 2 Carbon atoms should be separated from each other, and mixture II 11.1 to 100 to 50 mole percent of one or several aromatic or cycloaliphatic dicarboxylic acids and / or their derivatives and 11.2 from 0 to 50 mole percent of one or more aliphatic dicarboxylic acids having 4 to 12 carbon atoms and / or their derivatives consists. 2. Coating agent according to claim 1, characterized in that linear polyester with average Molar weights between 1000 and 2000 can be used. 3. Coating agent according to claim 1 and 2, characterized in that linear polyesters are used are, for the production of which a mixture I has been used that consists exclusively of Propanediol (1,2) and dipropylene glycol. The invention relates to liquid coating agents based on a mixture of binders and organic solvents or water and that Binder solubilizing additives ode, if necessary, on a solvent-free basis, which as binder