DE1805199C3 - Coating agents - Google Patents

Description

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 by esterification of the mixtures! and II have been produced, where Mixture I.

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

1.2 consists of 30 to 70 mol percent of diethylene glycol.

The invention relates to liquid coating compositions based on a mixture of binders and organic solvents or water and the binder solubilizing additives or optionally on a solvent-free basis that 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 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 is obtained combined with a linear polyester obtained by polyesterification of a dicarboxylic acid with a Diol of the general formula

and optionally up to 30 mole percent

Total amount of components 1.1 and 1.2

by one or more other aliphatic or 40 H- (OR) _m -O

cycloaliphatic diols in which the hydroxyl func-

tions are separated by 2 to 8 carbon atoms and, if appropriate, instead of up to 2 of the carbon atoms, oxygen atoms, which in turn should be separated from one another by at least 2 carbon atoms, can be replaced, Q- (RO) _n -H

j: .d mixture II

11.1 to 100 to 50 mole percent of one or several aromatic or cycloaliphatic dicarboxylic acids and their derivatives and

11.2 from 0 to 50 mol percent of one or more aliphatic dicarboxylic acids having 4 to 12 carbon atoms and / or their derivatives.

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 to produce a mixture! that has been used exclusively from Propanediol (1,2) and diethylene glycol consists.

is obtained in which A is a 2-alkylidene radical! with 3 bi:

4 carbon atoms means, R stands for an alkylene radical with 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 au: 2-ethylhexanediol (l, 3) as a plasticizer from extra homely value for use in urea-formaldehyde or melamine-formaldehyde condensates tion products described. According to this information;

The _{coatings obtained from S 5} are in some cases stretchable and impact-resistant, but too soft (see Comparative Example 2).

In addition, our own experiments show that mixtures of linear polyesters and a melamine are used in the case of these Formaldehyde resin were cured that the dabe

The coatings obtained are stretchable, but soft (see Comparative Examples 3 and 4).

From Houben-Weyl, methods of organi see chemistry (Vol. 14/2, pages 21, 22, 24 and 29) is dii Production of linear mixed polyesters known. Over it

6s addition, it is stated that these polyesters i.a. mi Aminoplasts can be crosslinked. A hint; that these products are processed into paint raw materials can be missing. In the same publication (page:

137/338) is shown that aminoplasts with polyesters of adipic acid / polyol or with unsaturated compounds such. B. monoglycerides of native fatty acids, can be elasticized. The last-called _[s reaction products are also used as coating agents. A reference to the use of linear polyesters - in particular those of a certain composition - in conjunction with aminoplasts as coating agents is not given in this publication.

From DT-PS 11 22 255 unsaturated ethers of aminotriazine / formaldehyde condensates are known which

Either as such or mixed with air-drying oils or other compounds polymerizable with peroxides, such as styrene or unsaturated polyesters, can be used for the production of trains , the crosslinking being accelerated by metal siccatives and possibly peroxides .

DT-PS 14 94 500 describes as an older Rechi coating agent made of acrylic ester copolymers and aminoplasts, which should contain up to 35 percent by weight of alkyd resins. It is expressly pointed out (column 1, lines 18ff.) That mixtures exclusively of alkyd resins and aminoplasts as coating agents have considerable disadvantages , that is to say, such mixtures are not claimed.

From US-PS 28 01 189, 29 31 739 and 32 07 623 linear polyesters are known, which, however, are not used in combination with aminoplasts . They are applied as such to glass fibers and are intended to serve as an adhesion promoter when the glass fibers are used as reinforcing material, e.g. B. be used in unsaturated polyester resins .

US-PS 33 92 135 describes the use of linear polyesters as plasticizers in crosslinked polyvinyl halide resins. The document can be taken at any point that the polyesters listed here arise in conjunction with aminoplasts excellent coating agent.

From GB-PS 6 76 372 electrical insulating varnishes, especially wire varnishes, based on polyesters of terephthalic acid, aliphatic dicarboxylic acids and ethylene glycol are known, which can optionally also be combined with other synthetic or natural resins, including aminoplast resins . These polyesters must have a molecular weight of 10,000 or more and are crystalline. For this reason, these polyesters are dissolved in solvents such as phenols or cresols to form relatively dilute solutions which, although common in wire enamelling, are undesirable in normal sheet metal coating.

From the US-PS 31 02 868 and 31 08 083 aqueous coating agents based on amino resins and polyesters are known whose essential components benzenetricarboxylic acids and optionally polyalkylene glycol monoalkyl ether-acids in addition to aliphatic dicarboxylic and aliphatic polyhydric alcohols. These polyesters are branched polyesters which, moreover, are only used in aqueous systems and are relatively expensive

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

This object has been achieved, surprisingly, in that coating agents have been found in which linear polyesters with an average molar of 1.2 ZU are used as component B

weights between 600 and 3000 are used have been prepared by esterification of mixtures 1 and II, with mixture 1

1.1 to 70 to 30 mol percent, preferably to 60 to

40 mol percent, from propanediol- (1,2) and 1.2 to 30 to 70 mol percent, preferably to 40 to 60 mole percent, composed of diethylene glycol,

ίο and optionally up to 30 mole percent, preferably up to 20 mole percent, the total amount of components 1.1 and 1.2 by one or more others aliphatic ^ or cycloaliphatic diols in which the Hydroxyl functions are separated by 2 to 8 carbon atoms and optionally instead of up to 2 the carbon atoms can be oxygen atoms, which in turn have at least 2 carbon atoms should be separated from each other, can be replaced,

and mixture il

11.1 to 100 to 50 mole percent, preferably 95 to 80 mole percent, from one or more aromatic or cycloaliphatic dicarboxylic acids and / or their derivatives and

0 to 50 mol percent, preferably 5 to 20 mol percent !, from 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 Carbon atoms are separated and optionally up to 2 of the carbon atoms are separated by oxygen atoms can be replaced, which in turn should be separated from one another by at least carbon atoms, are suitable e.g. B.

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-Ä thylhexanediol- (1,3), cyclohexanediol- (1,2), Cyclohexardiol- (1,4),

1,2-bis (hydroxymethyl) cyclohexane, 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, A, S-bis (hydroxymethyl) -

tricyclo- [5.2, l, 0 ^2b ] -decane,

where A 'stands for 3, 4 or 5, triethylene glycol, dipropylene 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, hexahydrophthalic acid, hexahydroisophthalic acid and endomethylene or endoethylene tetrahydrophthalic acid, hexachloroendomethylene tetrahydrophthalic acid or tetrabromophthalic acid

suitable, where the cycloaliphatic dicarboxylic acids can be used in their trans or cis form or as a mixture of both forms. The use of phthalic acid, isophthalic acid and hexahydrophthalic acid is preferred.

35

40

They are particularly suitable as aliphatic dicarboxylic acids Succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, decanedicarboxylic acid or 2,2,4-trimethyladipic acid. The use of aliphalic dicarboxylic acids with 4 to 6 carbon atoms, in particular 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, ι ο can also these are used, e.g. B.

Phthalic anhydride,
Hexahydrophthalic anhydride,
Tetrahydrophthalic anhydride, ι s

Succinic anhydride or glutaric anhydride.

Coatings with particularly good properties are obtained when using linear polyesters with minimal molecular weights from 800 to 2500, in particular from 1000 to 2000, which predominantly contain hydroxyl groups, ie have been produced with a molar excess of diol.

The polyesters can be prepared by all known and customary processes, with or without a catalyst, with or without passing through an inert gas stream, as solution condensation, melt condensation or azeotrope esterification, at temperatures of up to 250 ° C. or higher, the water released or the released A'kanole 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 polyester batches composed of η mol of diol and (n- \) mol of dicarboxylic acid is less than 7 mg KOH / g. In the case of batches of π mol diol and ('/ 7 + I) mol 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 losses of volatile substances remain 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 both the molecular weight of the polyester and its Composition have an influence on the properties of the paint films produced therefrom. At higher medium molecular weights, the hardness of the paint film is usually reduced, while the elasticity increases, on the other hand, in the case of low molecular weights, the flexibility of the paint film leaves with a simultaneous increase in hardness after. Differences in the composition of the polyester also have a similar effect: At higher proportion of aliphatic dicarboxylic acids and with greater chain length of the aliphatic dicarboxylic acids the elasticity of the paint film increases while its hardness is decreased. The reverse is done with 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-ended diols and with increasing proportion These diols in the polyester make the paint film softer and more flexible. However, if you use the Polyester additionally diols with short and branched carbon chains or with cycloaliphatic rings, the paint films produced from these polyesters generally become larger with an increasing proportion of these diols are harder and less elastic. Knowing these rules is easy possible, within the scope of the claimed range polyester with for the respective purpose to select optimal properties and use them for the coating agents according to the invention.

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. Tramethylol benzoguanamine, trimethylol mclamine or hexamethylenediamine, which can also be used in partially or completely etherified form, e.g. B. as Tetrakis (methoxymethyl) benzoguanamine, tetrakis (ethoxymethyl) benzoguanamine or polyether des Hexamethylol melamine, such as hexamethoxymethyl melamine or hexabutoxymethyl melamine. can be used be able.

However, it is also possible to check the miscibility between the resinous aminoplasts and those according to the invention to be used polyesters and their compatibility during stoving to improve that add certain amounts (up to 50 percent by weight, based on the total amount of solvent) of high-boiling polar solvents for both resins, such as z. B. ethyl glycol, ethyl glycol acetate, butyl glycol or cyclohexanone, or preferably polyester and aminoplast reacts with one another in a known manner in bulk or preferably in solution, care must be taken that the reaction does not proceed to crosslinking. This can e.g. B. by brief heating of the mixture or the joint solution of the two resins, if necessary in the presence of a catalyst, such as. B. organic or mineral acids can be accomplished. It isi it is also possible to use the polyester to be used according to the invention before or during production Aminoplast resins from e.g. B. urea, benzoguanamir or melamine and aldehydes to add to the approach it is of course also possible to additionally use customary alcohols to modify the alcohols formed in this way plasticized aminoplast resins are also to be used. DU methods for the production of such plasticized eggs Amine-aldehyde resins for both solvent-containing products as well as for aqueous paint systems are known.

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

To produce the coatings, polyester and aminoplast or theirs are usually first used

defined preliminary stages in common paint solvents, such as for example propanol, isopropanol, butanol, ethyl acetate, Butyl acetate, ethyl glycol, ethyl glycol acetai, butyl glycol, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone, trichlorethylene or mixtures of different 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 ι ο cuts, to be used as well. The amount of these less polar solvents used is within reasonable limits the solubility of the polyesters used according to the invention and their compatibility with the polyesters 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 be between 50:50 and 90:10, preferably between 65:35 and 85:15, vary; the optimal one for the respective application of the varnish The ratio can easily be determined by a few preliminary tests. It should be noted that often through Increasing the aminoplast content increases the hardness of the paint films and reduces their elasticity, 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.

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 varnish obtained is applied and fired at temperatures between 100 and 250 ⁰ C. The crosslinking reactions that take place are catalytically accelerated by acids. When using polyesters with a very low acidity, acidic substances can therefore be added to the paint strongly accelerated With larger Siuire - /. usut /, coatings that dry even at room temperature can be produced.

Even by converting a low-acid polyester (.0 with about 1 to 5% of an anhydride a relatively strong acidic dicarboxylic acid, / .. B. maleic anhydride, can the acid / number of the polyester can be subsequently increased and thus lower the burn-in temperatures even without the addition of strongly acidic substances. o.s

The crindimgsgemäU hcrgcselllen coatings have an abundance of good properties. They are high-quality, very easy to pigment and do not yellow. 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 150 ⁰ C according to the invention comprises coatings of as 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).

The provides an indication of the behavior of coatings in the event of sudden deformation so-called impact depth measurement. This measurement can be carried out, for example, with the impact deepening device 226 / D by the company Erichsen, Hemer-Sundwig. This device uses a hemisphere a radius of 10 mm due to a falling weight from the back of the paint into the sheet metal depressed. The depth can be varied by changing the height of the fall of the weight. It will be the Indentation value (in mm) indicated at which the lacquer layer begins to tear. (The ones in the examples values given were obtained in this way. In some examples the value is > 5mm specified because the device described is usually used with the Test used 1 mm thick drawing sheets, no deeper indentation possible.)

As with the description of the state of the art has been carried out and is proven by comparative tests, are already coatings made of linear polyesters and Aminoplasts known that are elastic and can withstand impact stress. These coatings but have very low hardnesses (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 characteristic picture opens up the coatings versatile application. In addition to painting individual parts that are exposed to impact stresses are, the painting of materials comes into consideration, which afterwards - / .. B. by punching - be deformed.

The polyesters used in accordance with the invention give low viscosity solutions. It is called paints with a high level of composite noise can therefore be processed, which saves work steps! can be excluded / .l.

Polyester production

A Danish from 5HHc l'ropandiol- (1.2) (5, I Mol : $ 18g diillhylene glycol (JMoI), 88Hg phthalic acid anh ;, drid ((ι mol) and 14 (i g of adipic acid (I mol) is unk

7 in the m

Stirring and passing a gentle stream of nitrogen according to the following 2'eit-temperature schedule heated 2 hours at 140 ° C, 2 hours at 160 ° C, 4 hours at 180 ° C, 4 hours at 19O ⁰ C and 26 hours at 200 ⁰ C. During this time, 134 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, pale yellow resin has an acid number of 4.6 mg KOH / g and a hydroxyl number of 62.1 mg KOH / g, which corresponds to an average molecular weight of 1,680. The polyester is dissolved in a mixture of 6 parts by weight of xylene, 1 part by weight of butanol, 1 part by weight of ethyl acetate and 2 parts by weight of ethyl glycol acetate 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 is completely dissolved, for 1 hour at 12O ⁰ C is heated, whereby the acid number of the polyester to 8.56 mg KOH / g is increased.

The acid number of a polyester is usually increased in the melt, but there are no difficulties in carrying out the same reaction in the solution of the polyester under the reaction conditions mentioned; It is, however, where y to ensure that the solvent does not contain any functional groups which may also react under the reaction conditions with the acid anhydride.

burns. To lower the baking temperature Lacquer solutions made using polyesters with a low acid number. 0.5% p-toluene sulfonic acid (based on the total detergent) 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 53 157, the Test of elasticity according to the methods described above. . Examples 1 to 7 are compiled in Table 1, including the type of used Melamine resin is specified. (In the column »Type of Melamine resin «means K that a butylated melamine-formaldehyde condensate was used, while HMM indicates the use of a hexamethylolmelamine derivative.) Table 2 contains the Test values for the coatings obtained from the polyesters described in Comparative Examples 1 to 4 below were manufactured.

Comparative example 1

^{1580 g of the symmetrical bis (hydroxyethyl) ether of bisphenol A (5 mol) are heated to 180 °} C. for 6 hours with 400 g of succinic anhydride (4 mol) while a stream of nitrogen is passed through. Remaining amounts of water of reaction are then removed by applying a vacuum of about 20 Torr. The polyester produced in this way has an acid number of 5 mg KOH / g; it is dissolved in a xylene-methylethylketone-cyclohexanone mixture (1: 1: 1) to form a 50 percent solution.

Manufacture of a lacquer

The solutions of the polyesters in suitable solvents, usually a mixture of xylene and a polar solvent, are mixed with a commercially available 55 percent solution of a melamine-formaldehyde condensate in a xylene-butanol mixture (1: 1) or with a commercially available hexamethylol amine derivative in the desired Mixed solids ratio. In order to set a polyester-to-mclamine resin ratio of 7: 3, for example 117 g of an oil percentage of the polyester are mixed with 54.5 g of the above-mentioned melamine resin solution; If polyester and melamine-formaldehyde condensate are not compatible with one another, the mixture of solutions - in the case of low-acid polyesters with the addition of 0.5% ρ-toluenesulfonic acid, based on the total amount of polyester and aminoplast - 10 to 60 minutes to up to K ) O ¹¹ C heated. _5S

Preparation of the paint color comparison example 2 (example 2 from the USA patent 24 60 186)

148 g of phthalic anhydride, 146 g of adipic acid, 278 g of 2-ethylhexanediol (l, 3) and 110 ml of xylene are within from 4 hours to 180 ° C and in a further 4 hours heated to 200 ° C., the water formed being separated off using a water separator. After that, will slowly distilled off the solvent within 4.5 hours, so that at the end a temperature of 240 ° C is reached.

For the initial installation of a
Hincle

pigme

Lacquer color becomes a Klarlaek in on 2: 1 with TiO /

entertained.

I lersldliiiH! and testing the coatings

To the

PrUiUiU 'will
hU.fhc iiiul G

ICM bzw.die clearcoat paint color attached mii laspliUten and a _K e-Vcrgleichsbeispicl 3

(Example I from Ulimann's Kncycloniklie der technical chemistry, 3rd edition, Bund 14th page 87, Urban & Schwatzenberg, Munich-Berlin, 1963)

1400 g of adipic acid (9.6 mol) and 675 g of ethylencnglycol (10.9 mol) are slowly heated to 130.degree. C. to 140.degree. C. while passing over a stream of nitrogen. In order to ensure that no glycol passes over when the water of reaction is distilled off, part of the water is returned to the column as reflux. In some hours I aufc the Reiiktionsgemiseh to 200 "C heated, then cooled aiii LWC and condensation under vacuum continued until it at 200 Torr and 200" C to ^r) is to H hours terminated. The waxy l'ulyeslci has a hydroxyl number of 54 mg KOI l / g and an average molecular weight of 2000; i ^% r will be in a '

11th

{ylol-methylethylketone-Gemiseh (1: 1) / u of a 50 per centigen Solution solved.

Comparative example 4

(Example 2 from Ullmanns Encyclopädic der technischen Chemie, 3rd edition, Volume 14, page Urban & Schwarzenberg, Munich-Berlin, 1963) g of adipic acid (2.16 mol), 480 g of phthalic anhydride (3.24 mol) and 374 g of ethylene glycol ( 6.5 Mo!) passing a feed among Sticksloffstromes slowly to 160 to 200 ⁰ C heated, are passed through 118 g of distillate. It should be ensured that the transition temperature at the top of the column does not exceed 100 ⁰ C. Then a further 19 g are distilled off in 6 hours with increasing vacuum. The polyester has an acid number of 3 to 4 mg KOH / g and a hydroxyl number of 56 mg KOH / g; he becomes in one

Xylene-methylethyl octone-cyclohexanone mixture (1: 1: I) dissolved to a 50% solution.

Table 1

At- polyester from

3PG *) 5DG *) 7 PSA *)

4 PG 4DG 6PSA 1 BSA *)

5 PG 3DG

6 PPE

1 ADS *)

3PG

3 DG

4 PSA 1 ADS

6 PG 4 DG 8PSA I ADS

2PG 2DG 2.5 PSA 0.5 ADS

4 PG 3 I) G 1 AG ') 6 PSA I BSA

MUt- weight ratio of mol- polyester to eeweight melaminhar /. ^e to TiOa

1630 70: 30: 0 70: 30: 80: 20: 80: 20:

1265 70: 30: 0 70: 30: 80: 20: 80: 20:

1680 70: 30: 0 70: 30:

1045

2120

820

1720

70: 30: 70: 30:

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

70: 30: 80: 20:

Type of

Melamine·

har / es

HMM *) HMM HMM K *)

HMM HMM HMM K

HMM HMM

HMM HMM

HMM HMM HMM

HMM HMM

Catalyst stoving condition
worked

70: 30: 0 HMM

70:30:50 HMM 80: 20: ¹ WHMM 0.5% pTS *)
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% IJ ¹ VS
0.5% pTS
0.5% pTS

Hardness deep drawing

according to ability

DlN after

53 157 DlN 53 15b

(sec) (mm)

130 ° / 30 '
130 ° / 30 '
130 ° / 30 '
130 ° / 30 '

130 ° / 30 '
130 ° / 30 '
130 ° / 30 '
130 ° / 30 '

130 ° / 30 '
130 ° / 30 '

130 ° / 30 '
130 ° / 30 '

130 ° / 30 '
130 ° / 30 '

190
156
162
157

170
165
152
146

178
161

156
148

130 ° / 30 '167
120 ° / 30 '151
130 ° / 30 '156

173
163

I 30 "/ 30 '165 1.30" / 30' l ^r > 4 130/30 '147

9.8> 1 7.3

> 1 9.7

9.2

9.8

9.2

9.2

> K)

Impact

(mm)

> 5

3-4 4-5 3-4

> 5

4-5

> 5

> 5

> 5

") Abbreviations:

1G lropii ()

IX; , .- Diiiihyliinglykiil I ¹ SA 'phthalic anhydride K, - Melanmi-lonnnUlehyd-Komuns.n

»IS · - p-ToluenesulfonsHiiri ·

HSA - lUTiistcinseurcaiihydncl

AI) S AG

ilen pure 1'olyeMci n.i

Adipic acid

Ähllyk

MaU-insUurcaiiliydriil

Table 2 Polyester from Mitt (Mole) = ßis- (hydroxyälhyl) -ethc Weight- Type of r of bisphenol-A condensate Kiitii- pTS Kinbrenn Hiirlc Deep drawing Pounding Vcr- leres 5 HÄBA *) 1880 = Succinic anhydride ratio Mclamin [ = Hxamethylolmclamindcrival lysatoi pTS conditional after lahigkcit ticfung equal- Mole 4 BSA ¹ ) = Mclamin-Fornialdchyd- Polyester too hiirzcs = 2-ethyl-hexanediol- (l, 3) pTS worked I) IN after example Weight 1.91 ÄHD *) 1750 Meiamin resin = Phthalic anhydride pTS 53 157 DIN No. 1 PPE *) to TiO: = Adipic acid
= Äthvicnclvkol 53 156 1 ADS *) pTS (lake) (mm) (mm) 10.9 AG *) 2000 70: 30: 0 K ») 0.5% pTS 130/30 ' 135 1.1 <1 I. 9.6 ADS 70: 30: 0 HMM ") 0.5% pTS 130730 ' 126 1.9 <1 6.5 AG 2050 70: 30: 0 K 0.5% pTS 130'730 ' 35 2.0 <1 2 3.24 PSA 70: 30: 0 HMM 0.5 ¹¹ Xi 130730 ' 19th > 10 > 5 2.16 ADS *) Abbreviations: 70:30:50 K 0.5 "/ (i 130730 ' 45 6.1 > 5 3 HÄBA 70: 30: 0 HMM 0.5% 130730 ' 39 8.8 > 5 BSA 70:30:50 K 0.5% 130730 ' 25th 7.9 > 5 4th K 70: 30: 0 HMM 0.5% 130'730 ' 22nd 9.1 > 5 HMM AND PPE ADS
AG

Claims (1)

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