DE1805182B - Coating agents - Google Patents

Description

The invention relates to coating agents on aminoplists and polyesters known whose essential

based on a mixture of bath products and borne components benzene tricarboxylic acids and

organic solvents or Wifeser and the optionally polyalkylene glycol monoalkyl ether as well

Binders water-solubilizing additives or aliphatic dicarboxylic acids and aliphatic

optionally also on solvent-free base polyhydric alcohols. With these polyesters

layer that acts as a binder is branched polyester, the one above it

In addition, only yes aqueous systems can be used

A. 50 to 10 weight percent aminoplasts and / and are relatively expensive.

or their low molecular weight, defined priorities from the German Auslegeschriften 1101667 and

stufen _le j 231 833 are solvent-free coating agents

and base of aminoplasts known that one thereby

B. 50 to 90 percent by weight hydroxylsruppenhal- «**! / That one

StS ^ ^ S ^ äSSMS JSI "Such removed überzu _f center!, Konntensich far

irSmatic and apophaticDicarbv ^ iures --already because of the difficulties with Arer her-

on the other hand position - do not enforce,

On the other hand, _Ay ^ _britischeQ Patent 676 372 & electron ind

in addition to customary additional and auxiliary insulating varnishes, especially wire varnishes, based on contain substances, the binder also by ao polyesters from perephathalic acid, aliphatic di-co-condensation of aminoplasts and / ode. carboxylic acids and ethylene glycol known, the gesederen low molecular weight, defined precursors with the least common with other synthetic or natural earths linear polyesters or resins borrowed from Mtschkonden, including aminoplast resins, sation of the starting products of Aminoplast Her- can be combined. These polyesters must be The position produced with the linear polyesters resulted in a molecular weight of 10,000 or more can be. srcund are crystalline. Hence these become polyesters

From the German Auslegeschrift 1122 255, unsaturated ethers of aminotnazin-formaldehyde- relatively dilute solutions are dissolved in solvents such as phenols or cresols, which are known for condensates, which either as such or wire enamelling are common, for normal sheet metal but in a mixture with air-drying oils or paintwork is undesirable,
Their compounds polymerizable with peroxides are known from German patent specification 1 015 165, like styrene or unsaturated polyesters, by hardening a mixture of coatings, whereby the phthalic acid - fumaric acid - propylene glycol polyester crosslinking is promoted by metal siccahve and possibly on the one hand and a butylated melamine-formaldehyde peroxide. On the other hand, to produce coatings from the British patent 35 hyd resin,
Document 1 000 534 is a special process for the manufacture of the new paint films obtained have a low level of unsaturated polyester known, which is resistant to mixing.
Copolymerization with Vinylvetbindungen, especially White styrene can be hardened from the German patent specification 1015 165 and thus also known that one is chemically extremely leveled for the production of coatings. The 40 resistant coatings are used if a coating agent in these documents is based on other alkylated melamine formaldehyde or urea starting materials and are combined with a completely different formaldehyde condensation product using a line mechanism that cross-links a polyester that is combined by polyesterification

From U.S. Patents 3,102,868 and a dicarboxylic acid with a diol of the general

3108 083 are aqueous coating materials based on 45 formula

H - (OR) »- O - ^ ~~ V ~ A - / ~~ \ _ © - (RO) _n - H

is obtained in the i \ tm 2-AlkjlidenradikcJ with 5 ^ 9 In addition, our own experiments show in which 3 to 4 carbon atoms läcdcj'if. J? for eui alky- ^v mixtures of linear Polvestern and a metal radical with 2 to 3 KchScnstcITatoT ^ n stands, min-Fonnaldeh> d-Harz were hardened, that the m and π jiv.c! s most often were obtained from the S-icme Coatings stretchable, but from m and η not % zJZsx as 3 i ^ t Dal.?! know are soft (see Vergelicbsbeisplele 3 and 4).
also linear Po '> csier from Ger ^ I co tl ^ raitirer 55 The invention is based on the object of producing over-diols mitelnar.der or nut kleL: ercn Mbt ^ ^ «fs- 7 -jge in which high elasticity with between two different alcohols. D: unite our great hardness. In a number of such over-the-counter applications (P 16 95 512.7, P 16 95 513.8, they are hard, they are very brittle (see comparisons - P 16 44 761.3, P 16 44 764.6, P 16 44 766.8, game 1). 60 P16 44 769.1) has already been proposed, this poly task through the use of polyesters or copolyesters from 2-AÜ)% L ^v exan-J] o ! - (l 3) ais Wcc ^ Trc ^ er meren from very special selection to solve jproducts, from exceptional value for d: e, \ eλc. ter.g now in this task da-Harn5toiT-Forr was surprising: i ¹ di>) d- or Me '^ Tin-Forraalde- solved by that coating compositions wuiden found hjd-Kondensaüo ^ prciiikten described. According to 65, in which linear polyesters are obtained as component B with these data, was at the mean molecular weight between 600 and 3000 one-part stretchable and impact-resistant i> er za soft (s are displaced by esterification of the Mixtures the same - p.el 2). "and Π have been made skid, where mixture I

1.1 to 70 to 30 mol percent from ethylene glycol Instead of the free dicarboxylic acids, t "" ¹ their esters with short-chain alkanols, e.g. di-

1.2 to 30 to 70 mol percent of propanedio (1,2) methyl, diethyl or diprop / lester, who are used

the. If the dicarboxylic acids form anhydrides,

and optionally up to 30 mole percent of 5, these can also be used, e.g. B. total amount of phthalic components 1.1 and Ϊ2 säureanhydrid.Hexahydrophthalsäureanhydrid.Tetrickt one or more other abphatic or hydrophthalic anhydride, succinic anhydride, cycloaliphatic diols, m which the hydroxyl func- tional glutaric anhydride or maleic anhydride are separated by 2 to 8 carbon atoms Properties

and optionally at Sv; Ue of up to 2 dei carbons when using linear polyesters with material atoms oxygen atoms can stand, the mean molar weights between 1000 and 2500, in turn by at least 2 carbon atoms from one another - exclusively ethylene glycol and propanediol- (1,2) should be separated from others, be replaced, and as a diol component and predominantly hydroxyl group Unfold the mixture, i.e. with a molar excess

_. _ftl ... ,, .-. . . 15 have been made on Diel.

Π.1 to 91 to 33 mol percent from one or more- _Κβ production of the polyester can after all rencycloahphatepicarbonsauren, in which known and customary processes, with or without the carboxyl groups in the 12- or 1,3-position catalyst, with or without passing a Inertangeordnet sirnd, or aromatic dicarboxylic gas stream, as a solution condensation, and Schmelzkonsauren or derivatives thereof ao-condensation or azeotropic esterification, in ^{temperature-1111 (1 3} temperatures up to 250 C higher evter performed advertising

Π 2 to 9 to 67 percent of the "iner or meh- ^den " ^{whereby the} resulting water or this free

y ν, ti h r »-ίν>. ""'"* j ™ ¹ ; the alkanols are continuously removed.

1nY ~ u1J.-t ~ .it t _- "jj j τ-. · 5 The esterification proceeds almost quantitatively and can

12 carbon atoms rad or their derivatives _{a $ by determining the} hydroxyl and acid numbers

exists to be pursued. As a rule, the esterification AIs are selected in subordinate amounts of concomitant use in such a way that the reaction possible diols in which the hydroxyl functions is complete by 2 to 8 carbon atoms, that is, until the acid number of 8 carbon atoms is separated and, if necessary, ester may be replaced is Ansatzen from η mole of diol and (n-l) mole to 2 carbon atoms by oxygen atoms 30 dicarboxylic acid is less than 7 mg KOH / g, which in turn by at least for pools of η mole of diol and (n4-l) mol Di-2 carbon atoms should be separated from each other, carboxylic acid is esterified until the hydroxyl properties are, for example, propanediol (1,3), butanediol (1,2), number below 7 mg KOH / g The molecular weight of butanediol ( 23), butanediol- {1 ^), butanediol- (1,4), polyester can be easily obtained via the Em-2,2-dimethyl-propanediol- (1,3), hexanediol- (1.6), 35 composition ratio regulate of diol and dicarboxylic acid. 2-Ethylhexanediol- (1,3), Cyclohexanediol- (1,2), Cyclo- The esterification temperature is chosen so that hexanediol- (1,4), 1,2-bis- (hydroxymethyl) -cyclohexane, the losses volatile substances «low!, S-bis-ihydroxymethylj-cyclchexane, 1,4 · bis - (tr * · remain, ie, at least during the first period of hydroxymethyO-cyclohexane,; r, 8-bis (hydroxymethyl) space of the Esterification is tricyclo-IS ^ 10 ^ l-decane at a temperature, where χ for 3, 4 or 5 40, which is below the boiling point of the lowest, diethylene glycol, triethyl glycol, dipropyleneglycol, glycol or propylene glycol. Cycloaliphatic In the production of the polyesters it should be noted that diols can be used in their cis or trans form or as both the molecular weight of the polyester and a mixture of both forms, the composition of which influences the intrinsic aromatic or cycloaliphatic dicarbonic shafts of the lacquer films made from it, acids are z. B. phthalic acid, isophthalic acid, tetra- At higher average molar weights, the hardness of the paint film is reduced in the hydropthalic acid, hexahydrophthalic acid, hexahydro- rule, while isophthalic acid and endomethylene or endo, on the other hand, reduces the elasticity with lower ethylene tetrahydrophthalic acid, hexahydrophthalic acid - Molecular weights of the flexibility of the paint film in the case of len-tetrahydrophthalic acid or tetrabromophthalic acid 5 «while increasing the hardness at the same time. Similarly suitable, whereby the cycloaliphatic dicarboxylic modes also have an effect, differences in the additional acids in their trans or cis form or as a mixture composition of the polyester · With a higher proportion of both forms can be used. The comparison of aliphatic dicarboxylic acids and, with greater turns, of dicarboxylic acids, in which the carbon chain length of the aliphatic dicarboxylic acids increases, oxyl groups are arranged in the 1,2-position, the elasticity of the lacquer film increases, while its hardness is special of phthalic acid and hexahydrophthalic acid , is decreased. Conversely, increasing is preferred. Proportion of aromatic and / or cycloalphatic aliphatic dicarboxylic acids are particularly suitable dicarboxylic acids in the polyester the lacquer film harder and succinic acid, Glvtarsure, adipic acid, cork less flexible. Acid, sebacic acid and decanedicarboxylic acid exert a similar kinetic flow. or 2,2,4-60, if necessary with% other diols: TrimethyladipinVaure. With increasing chain length of these saturated dicarboxylic acids, such as Moiem open chain diols, and with increasing proportions of acid, fumaric acid, itaconic acid or citric acid, this D: o) s in the polyester becomes the lacquer film can be used softer, but the vervtndur-g is sown and more flexible. However, does Hertiger use aliphaüscher dicarboxylic acids rm 4 b? 6 lioh- 65 the polyester additionally diols with short lenstoffaiomen, in particular the Av *. ■ ^> in ^! Äx. «t or and \ branched carbon chains or with cjcloeinfts e; wa 1: 1 mixture from Acirau« ·? and aliphatic rings, the lacquer films produced from these poly-succinic acid, preferably "esters, are usually

increasing proportion of these diols harder and less- ethyl acetate, butyl acetate, ethyl glycol, ethyl glycol j

ger elastic. If these rules are known, it is without acetate, butyl glycol, methyl ethyl ketone, methyl iso-j

Difficulties possible in the context of the claimed butyl ketone, cyclohexanone, trichlorethylene or \

th range of polyester with for the respective «mixtures of different such solvents,!

Optimal properties for the intended use to be selected 5 solved It is of course also possible and!

len and recommended for the appropriate coating agents for economic reasons, more j

to use. or less large amounts of polar solvents, j

Suitable aminoplasts are the known such. B. benzene, toluene, xylene or higher boiling <* r Conversion products of aldehydes, in particular aromatic cuts, to be used as well. The j Formaldehyde, with several amino or amido xo amounts of these less polar solvents

group-bearing substances, for example with melamine, within the scope of the em- " ₍

Urea, dicyandiamide and benzoguanamine, in set polyester and their compatibility with the Ask. Mixtures of such aminoplasts used can also be selected as desired; she can Products. Particularly suitable are those with A''io ~ often a proportion of up to 80 ° / · and more in the Lö-;

pick up modulated aminoplasts. 15 solvent mixture e.paking. ",

Due to the sometimes only limited compatibility when using polyesters with a high acid number,

these resin-like products with the invention that is to say with polyesters that have a larger number _;

Polyesters to be used will preferably have the non-esterified carboxyl groups, it is ₍

Low molecular weight, defined precursors of amino "of course also possible, aqueous solutions

plastic that can be used with the invention. This can be done according to the well-known and '

the polyesters are practically indefinitely miscible, customary methods take place, with de. · As a rule, the

used. Such defined precursors of amino carboxyl groups with completely or partially

plastics are z. B. tetramethylolbenzoguanamine, tri-amines are neutralized and possibly also

methylolmelamine or hexamethylolmelamine, which are also water-miscible solvents. J

also in partially or completely etherified form, e.g. B. »5 are used, which serve as solubilizers. ;

"~ ils Tetrakis- (methoxymethyl) -benzoguanamiri, Tetra- It is of course in the manufacture of

kis- (ethoxymethyl) -benzoguanamine or polyether aqueous lacquer solutions required, soluble in water

of Hexamethylolmelamifl, such as Hexamethoxvmethyl- borrowed aminoplasts to be used; The defined pre-melamine, or hexabutoxymethlymelamine, levels of aminoplasts are also used for this purpose

can be. 30 particularly suitable i

However, it is also possible to determine the miscibility between the resin-like aminoplasts and the polyester to be used according to the invention, preferably between 50:50 and 90:10, as well as 65:35 and 85:15, vary; The optimal improvement for each of the compatibility during baking due to the occasional intended use of lacquers, that the mixture of the solutions from 35 ratio can easily be determined by a few preliminary tests polyester and aminoplast certain amounts (up to. It must be taken into account that often 50 percent by weight , based on the total amount by increasing the aminoplast content, the hardness of solvent) increases in high-boiling polar Losem of the paint films and their elasticity verminfür both resins, such as. B. ethylglycol, Äthylglykol- is changed, while lowering the Aminoplastacetat, butyl glycol or cyclohexanone, or 40 added portion subsides, the hardness and flexibility zi £ but preferably polyester and aminoplast in existing take t, known manner in bulk or preferably in the The total binder content of the lacquers can be reacted with one another per solution, whereby care must be taken within the usual limits, depending on the intended use, that the reaction does not fluctuate to the point of crosslinking. } tation progresses. B. by short-term 45 The paints can contain the usual additives and auxiliary 'heating of the mixture or the common substances, for example pigments, Vfiriauf solution of the two resins, optionally in antidotes and additional other binders, such as ζ Β. waiting for a catalyst, such as B. organic or epoxy resins and hydroxyl-containing silicone mineral acids, are accomplished It is resins. It is also possible to use the 50 according to the invention. The varnish obtained is applied and, in the case of temperature: polyester, is baked between 100 and 250 ° C. even before or during manufacture. The amino resins from z. B. urea, benzo thereby occurring crosslinking reactions; guanamine or melamine and Alde'mden through the approach, acids catalytically accelerated. When used, it is of course also possible to add polyesters with a very low acid number, in addition to alcohols for modification of the lacquer, acidic substances can therefore be added to the lacquer. If you add 0.5 ° / Ό, for example, you use; Methods for the production of such p-toluenesulfonic acid (based on the total bond plastified Aj "ir" aldehyde resins for both mediums) the crosslinking is greatly accelerated. Solvent-based as well as water-based paint systems are known. 60 Produce coatings that dry at room temperature. ·

For combination! »Titled the in accordance with the invention, also through implementation of a low-acid poly-

set polyester sfribea a large number of commercial esters with about 1 to 5% of an anhydride of a relative

licher aminoplasts hr ». whose defined precursors are strongly acidic dicarboxylic acid, e.g. maleic acid

available. ; anhydride, you can get the acid number of the polyester

For production, <& * coatings are usually increased subsequently to 65 and so without the addition of

first of all polyester and aminoplast or its strongly acidic substances the stoving temperatures

nated precursors ^ »« common paint solvents, such as lowering,

for example, J ^ v | ttnol. isopropanol, butanol, The coatings produced according to the invention have

«It. M ' »

₍ 1805 lflfe.

7 \ J 8

an abundance of good properties. They are high · ι PnWct » t, « η t
shiny, very easy to pigment and excellent roiyesternersieiunp
fixed payment. If the coatings of A mixture of 192.2 g "ÄthyIenglykol (3.1 mol), heat aging of 72 hours at 100 ⁰ C sub 304 g Fropandlol- {1,2) (4MoI), 592 g Phthalsäurezogen, so is not detect visible yellowing; S aohyorid (4 mol), 146 g <"ριη $ αυΓβ (1 mol) and also a heat aging of 72 hours at 150 ° C 100 g succinic acid additive (1 mol) is shown the coatings according to invention as agü- stirring and Durchleitcn a weak Stickstoffbungsbestandig out. The coatings are stable current n2ch the following time-temperature schedule ergegenüber solvents such as xylene, gasoline benzene hitzU 2 hours at 140 ⁰ C, 2 hours at 160 ⁰ Q mixtures, esters and ketones. in hiaius io they have 4 hours at 180 ⁰ C, 4 hours at 190 ⁰ C and a good acid and Alkalibestandigkeit 16 hours at 200 ° C. In this time insauf. In Salzsprühversuchen, tropical tests and Prü- total 122 g of water separated. Subsequently, levies weatherometer they exhibit heivor- is 15 minutes bej 200 ⁰ C and a superior Korrostonsschuüwirkung and Wetterbestan- vacuum of 20 Torr stirred. Since & clear colorless speed 15 resin has an acid number of 3.2 mg KOH / g and the berausragends te property of the invention has a hydroxyl number of 79.9 mg KOH / g, what is according to the coatings produced, however, their large mean molecular weight of 1350 de-elasticity with high hardness. The polyester is in a mixture of The elongation behavior of coatings is described as 8 parts by weight of xylene, 1 part by weight of butanol and comfortably by adding 1 part by weight of ethyl glycol acetate to a 60% cupping test (according to DIN 53 156) and solved as a solution
Measure of the extensibility the deepening of the painted

Sheet in now indicates in which the lacquer layer increases the acid number of a polyester
tear begins. Essential for this test procedure

is that the deformation of the coating slowly »5 to melt ^e: nes polyester having a low acid If (feed mm'Sek x 0.2.). 1.2 · / · maleic anhydride (based on an indication of the behavior of over- to pure polyester) are given. After the coatings at ZnJ sudden deformation provides compound Anh> is completely dissolved dnd, 1 hour, heated to the sogcnannle Schlagticfungsmessung These MES 120 ⁰ C, whereby the acid number of the PoIysung may, for example with the 30 Schlagtiefungs- ester to 8.56 mg KOH / g is increased.
J gerat 226 / D from Eriehsen, Herner-Sundwig, The acid number of a polyester will be determined. With this device, * me is usually carried out in the melt, but a hemisphere with a radius of 10 Jim through a hemisphere with no difficulties, the same reacppearance. Weight from the back of the lacquer finish in the solution of the polyester under what is called the sheet metal suddenly impressed. Duich changed the reaction conditions to be carried out; The height of fall of the weight must be determined, however, care must be taken to vary the solvent fungus. The indentation value (in mm) contains the functional groups specified under the j where the varnish layer is allowed tear the said reaction conditions also with the start. (The values given in the examples can react with anhydrous anhydride,
were obtained in this way. In some examples, 40

len, the value> 5 has now been tackled, since the process of producing a lacquer
; level device with the usually tested

The solutions of the polyester in suitable solution

Cupping allows), usually a mixture of xylene and

^; As with the description of the prior art 45 of a polar solvent, a purchase

was carried out and, through comparative experiments, a 55% solution of a melaniin-formaldehyde

is known, there are already coatings made of linear poly-condensates with a xylene-butanol mixture (1: 1) or

Esters and aminoplasts known, which are flexible with a commercially available Hexair.ethyfolmelanJnderivat

'and also to an impact load. mixed in the desired fuel ratio. To ei »

! However, these coatings have a very low Hanen 50 polyester-melamine resin ratio of 7: 3.

; (according to DTN 53157) on the other hand are coatings, for example 117 g of a 60% igea

high hardness known, but they are not elastic. Solution of the polyester with 54.5 g of the mentioned

In this way, the herbal resin solution according to the invention has been mixed, should upholstery be used

tcncn coatings both high elasticity and a min-formaldehyde condensate do not combine

, great hard on. The mixture of solutions will be sustainable

! This property profile opens up the coatings - with low-mud polyesters with the addition of 0.5%

a versatile application. In addition to the paint, p-Toluolsulfonsaurc, based on the total amount

of individual parts, the impact loads from polyester and aminoplast - 10 to 60 minutes

the paintwork is heated to between 50 and 100 ° C

The poly- For the production of a lacquer color is used according to the invention a clear ester result in low viscosity solutions. It contains lacquer in a binder / pigment ratio of 2: 1 Paints with a high TiO solid content, pigmented, should therefore be used

^ Αϊ? ™ ^{1 V0} "^ ¹⁵⁸ " ⁸ " ^iS " Η »** -d exam dc, O ***

Downsizing ⁴ e Examples of the further explanations For testing the clear lacquer or the lacquer

Invention of the invention: paint is applied to test panels and glass plates

(ο

ίο

and baked To reduce the Einbrenntemperatui is Lackiösungen, the lower SkurezaH esters using Pol} were prepared, 0.5 ⁰ Zo p-ToIuokulfonsäure (based on the total binder) was added, the layer thickness of the S film, on which the check is made betragi in all examples 40 to 60 μ. The hardness test is carried out according to DIN 53 157, the elasticity test according to the methods described above.

Examples 1 to S are listed in Table 1 in Russian set, including the type of melamine used. is specified. (In the column »Art of the melamine resin, K means that a buttered Melamine-formaldehyde condensate was used, while HMM the use of a Hej.amethylol- ij melamindenvats.) Table 2 contains the Test values of the coatings resulting from the following Comparative Examples 1 to 4 described polyesters were manufactured.

go comparative example 1

1580 g of the symmetrical bis (hydroxyethyl) ether of bis-phenol-A (5 mol) with 400 g Succinic anhydride (4MoI) as well as passing a one piece of current flows for 6 hours at 180 ° C heated. The remaining amounts of water of reaction are then removed by applying a vacuum of removed about 20 torr. The polyester produced in this way has an acid value of 5 mg KOH / g; he will in a xylene methyl ethyl ketone cyclohexanone Gs- 3 » mixed (1: 1: 1) dissolved to a 50% n solution

Comparative Example U

(Example 2 from U.S. Patent 2,460,186)
148 g of phthalic anhydride, 146 g of adipic acid, 278 g of 2-ethylhexanediol (l, 3) and 110 ml of xylene are heated to 180 ° C rad in a further 4 hours to 200 ° C, the water formed over a water separator is separated. Thereafter, the solvent is slowly 4 »the solvent a
Temperature> on 24G ^C C

ΐ. so that at the end an i.twwd.

(Example 1 from UflnreT.s Encykolpädie

der techz ^ cioi Cier ^ e, 3rd edition, vol. 14, p. 87,

Urban & Schwarzenbsrg, Make — Berlin, 1963)

140Cg adpic acid (9.6 Mc!) And 675 g Ethyleogiykol (10.9McI) are heated x =: jst transferring a SnckstoSstronies latcsasi a = i 130 to 140 ° C. passes = h, a portion of the distillate is given zh Rlcilauf to the column. In the course of a few sciads the reaction powder is cooled to 200 ^: C enL: zt, then to 150 ⁰ C and the kocdenss ^ ea continued under vacuum until it is finished at 2CO clay c = d 200 ° C after 5 to 8 hours. -axh-like polyester has a hydroxyl number of 54n; KOHg and an average molecular weight of 2030; it is in an X>lol-Meüi>'iämylke ^ 53-Ge = iäcb. (1: 1) dissolved to a 50% solution.

(Example 2 from UIIr ^ -cs Encyklopädie der tecrm'.srhen Cheraie, 3rd AuOage, Vol. 14, p. 87, Urban & Sdrwarzecberg, h'.Zz-zbso- Berlin, 1963) 316 g of adipic acid (2.16 } <oT), 480 g of Phlhalsäureanljdnd (3 ^ 4MoO and 374 g of ethylene glycol (6 ^ moles) "ground vzicr € 'oerk: tcn a stream of waste slowly heated to 160 ° -J-C, until 118 g of distillate are Cbergeganrca -erbei is important to ensure the DAB Cbergangsrr; nichTüberci gt temperature-at the top of column 100 ^C C Subsequently, at ctekendem vacuum α 6 hours still 19 g abdestüirt the PoS ester hai a Saurczahl 3-4 mg KOHg ens and hydroxyl. of 56 mg KOK g; it is dissolved in ice in xy'ol-methylethylkiton-cydobexanone-Gemlsca (1: 1; 1) to a 50% solution

Table I.

polyester
from [mol] feres
Mole Weight Type Je »
Melamia catalyst 130 ° / 30 ΗΪΛί Ti ^ rich- Impact
testing example Weight ratio
Polyerter too
Melammhaiz 130 ⁼ / 3O ' 53Ü7 ability
after
DIN ΐ3156 [min] 2 AG *) 680 to TtQz HMM *) 0.5ViPTS *) 130 = / 3ir tsecl [met] 4th 1 2 PG *) 70:30: 0 HMM O ^ V. pTS 135 8.8 4-5 2 PPE *) 80:20: 0 HMM 0.5 »/» pTS 140 ^o / 30 * 121 9.7 3- * IADS) 80:20:50 140 ⁰ / 3Cr 12S 7.2 3AG 1270 HMM 0.5 · /. pTS 140 ^c / 3O * > 5 2 3PG 70:30: 0 HMM 0.5 ·. '. pTS 140 ° .'3O ' 161 > 10 > 5 3PSA 80:20: 0 HMM O ^ '. PTS 140 '/ 3C 143 > 10 4-5 2ADS 70:30:50 HMM 0.5 * / »pTS 14O ^c , GCr 152 > 10 5 4 / SG 1430 80:20:50 HAfM O ^ V. pTS 130 ^ 3CT 13S > 10 > 5 3 4PG 70.30: 0 HMM 0.5 '/. PTS 130 ", '3O' I ^ > 10 > 5 5PSA 80:20: 0 K ») 0.5 '/ »pTS 14O ° / 3O ' 16+ > 30 4-5 2ADS 70:30: 0 K 12 »/.MA·) 140 ^3/30 * ιει 9 »5 > 5 80:20: 0 HMM 0.5 ^e /.pTS 140 ° / 3Cr 173 > 30 4-5 3 AG 2330 75:25:50 HMM QJS *!% J) TS 140 ° / 30 ' 1-iS > 30 > 5 4th 7PG 70:30: 0 HMM 0 ^% pTS "lsiT "> 10 > 5 6PSA 80:20: 0 HMM O ^ '/. PTS 175 > 30 1.5ADS 80:20:50 4-5 US BSA *) XZ.L »= - ■ Footnotes at the end of the table

SK

ϊ; ,, 1 806 182 ι

Table 1 (continued)

example Pole estei
EUi [mole] Mitt
leres
Mole
Weight Weight
"ΐ vertühltnii
Polyester too
Melarmnhar?
zuTiO » Type of
melamine
resins * KaUl) ¹ SBtOr Burn-in
conditions hardness
naf '»
Dirt.
53157
[lake] "deep drawing
ability
after
DIN 53156
[mm] Ski «·
deepening
[mm] 5
6th
7th
8th 4AG
9PG
8PSA
2 ADS
2BSA
4AG
3PG
4PSA
IADS
IBSA
3 AG
4PG
4 PPE '
IADS
IBSA
4AG
4PG
IDG ·)
6PSA
IADS
IBSA 2810
1500
1350
1670 70:30: 0
80 20: 0
80:20:50
70:30: 0
80:20: 0
80:20: 0
80:20:50
70.30: 0
80:20: 0
80:20:50
70:30: 0
80:20: 0
80:20:50 HMM
HMM
HMM
HMM
HMM
K
HMM
HMM
HMM
HMM
HMM
HMM
HMM O ^ '/ opTS
0.5% pTS
0.5'yopTS
o! 5 »/» pTS
0.5 "/ opTS
0.5 «/ opTS
0.5 ° / opTS
0.5VopTS
0.5 "/" pTS
0.5 x / pTS
0.5 «/ epTS
0.5 * / »pTS 140730 '
140730 '
140730 '
140730 '
140730 '
130730 '
140730 '
140730 '
14073ff
140730 '
14073C
140730 '
14073C 178
160
145
181
176
179
153
192
184
176
173
165
148 8.8
> I0 > 5
> 5
> 5
> 5
4th
> 5
> 5
> 5
4th
4-5
> 5

} Abbreviations:

AO = ethyl <»glykoL PG β PropaaSoMU). PSA = phthalic anhydride, ADS = adipic acid HMM = hexamethylobnelamine divaL K = melamine-formaldehyde condensate

pTS = p-toluenesulfonic acid.

MA s maleic anhydride.

(The acidic polyester is thrown) reaction using the specified amount of maleic anhydride - based on the pure polyester - according to the method described brought a higher acid number) BSA s succinic anhydride.

DO s DiathyknglykoL

Polyester from [mol] Mitt
leres
Mole
Weight Weight"·
ratio
Polyester STi
Melamtnhairz
to TiOt Table 2 catalyst Embrenc-
conditions Hardness
after
DIN
53157
[sec] Tic & ieh *
capability
n.Bch
Dm
53156
[well] Sliding
deepening
[mm] I.
Vcr-
equal
example
No. 5HÄBA *)
4BSA »)
1.91 ÄHD *)
IPSA *)
. IADS *)
10.9 AG *)
9.6ADS
6.5 AG
3.24 PSA
2.16ADS 1880
1750
2000
2050 70:30: 0
70:30: 0
70:30: 0
70:30: 0
t
70:30:50
70:30: 0
70:30:50
70:30: 0 Type of
Melamine-
resin 0.5 «/ epTS
0.5 "/ opTS
0.5 »/» pTS
0.5 «/.pTS
0.5 «/ opTS
0.5 »/ epTS 130730 '
130730 '
130730 '
130730 '
13073O *
130730 '
130730 '
130730 ' 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 1
2
3
4th K *)
HMM *)
K
HMM
K
HMM
K
HMM

*) Abbreviations

HABA = bis (hydroxyäthyD -ether des Bispbenois-Ä. BSA = succinic anhydride

K = Melamm-Formaldehyde-Condensate HMM = Hexamethylolmelamindenvat.

. EXAMPLE 9l 1_

The polyester of Example 1 is at room temperature without the addition of solvent with a commercial hexamethylol melamine derivative (HMM), in

AHD = 2-Aüiyl-hexanedioHl ^).

PSA s phthalic anhydride. ADS = adipic acid.

AG = ethylene glycol

which the required amount of p-toluenesulfonic acid is dissolved, mixed from these mixtures KlaTlack films with a wet layer thickness of about 60 to 70 μ produced and baked for 30 minutes at J 40 ° C. Burned-in clearcoat films on one

Claims (5)

1 80S mixed aia 70 parts by weight of polyester, 30 parts by weight of melamine derivative and 0.5 parts by weight of p-toluene sulfonic acid have a hardness of 107 seconds with a deep drawability of 10.7 mm and an indentation of 3 mm, while baked clear lacquer film from a Mixture of 80 parts by weight of polyester, 20 parts by weight of melamine derivative and 0.5 parts by weight of p-toluene sulfonic acid with a hardness of 102 seconds, a deep elongation of 10 mm and a blow hole of> 5 mm. After adding only 10 percent by weight of ethyl glycol acetate to the clear lacquer, stoved films are obtained whose properties correspond completely to the films described in Example 1. In the case of pigment-deep paints, an addition of only 5 percent by weight of ethylglj kolacetal air * is sufficient to obtain films with the values given in Example 1. Material flow after heated: 2 hours 4 hours at 180 42.5 hours at 2 total 88 g of water, resin has a seed, a hydroxyl number, a mean speaks ο 171 g of this bottom! of the melt at 140 ° C, 2 hours at 160 ° Q IC, 4 hours at 1900 ° C and \ ° C. During this time, divorces are made. The clear, colorless index of 6.85 mg KOH / g and too 58.95 mg KOH / g on what is lekulargewjcht of 1710 contained resin (C, 1 mol) are in O0C with stirring with 28 g of phthalic anhydride (0.19 Mol) converted. After a reaction time of 4 hours, an acid temperature of not , 2 Example 10 water added, ν solids content vo value of 7.2 and «o (DIN cup no. <A mixture of 186 £ ethylene glycol (3 mol), 228 g propanediol <1.2) (3 mol), 723.5 g of phthalic acid additive (4.875 mol) and 164.25 g of adipic acid (1.125 mol) are added until an acid number 5 of 69.45 o * g KOH / g is reached with stirring and by widening a weak flow of nitrogen according to the following rule -Temperature Pl & n condensed: 2 hours at 140 ° C, 2 hours at 160 ° C, 4 hours at 180 ° C, 4 hours at 190 ° C and 8 hours at 200 ° C. The clear, colorless resin has a hydroxyl number of 59.35 mg KOH / g on; au The hydroxyl number and acid number are calculated to have an average molecular weight of 870. 174 g of this polyester resin (0.2 mol) are mixed with 20.2 g of ethylamine (0.2 mol) at 85 ° C. and then 74 g of isopropanol and then 80 g of water were added, resulting in a clear, colorless solution with a solids content of 50 percent by weight and a pH of 7.45. 4 · This solution, which remains unchanged for several months, can be diluted with water as required after the pH value has been adjusted to 8.5 to 9. This aqueous powder solution and a commercially available hexametine / olmelamine derivative (KWtM) are used to produce clear lacquers which are pigmented with TiO2 in a biodegradable pigment ratio of 2: 1 and adjusted to a solids content of 60 percent by weight with water. The films made from this paint are baked at 1803 C for 30 minutes. are smooth and shiny. The stoved coatings, which contain a mixture of 70 parts by weight of polyester and 30 parts by weight of melamine hat as a binding agent, have a hardness of t30 seconds, a deep drawability of 9.4 mm and a depth of 3 to 4 mm, while the coatings, the binder of which consists of 80 parts by weight of polyester and 20 parts by weight of melamine derivative, has a hardness of 123 seconds, a deep-drawability of 10.1 and an impact of 3 mm. Example 11 A mixture of 99 g of ethylene glycol (1.6McI), 266 g of ProFandioHl, 2) (3.5 mol), 444 g of phthalic anhydride (3 mol), 109.5 g of adipic acid (0.75 mol) Tind * 75 g succinic anhydride (0.75 mot) is diluted to 8.5 bi as desired while stirring and passing through a weak stick-wen. Holds 60 Gewi sea lacquer colors baked at 180 ° C. The baked-on coatings, which are the main poly methylol melamine with a hardness of 10.2 mm, while 80 parts by weight are a melamine derivative, a clear solution with a 50 weight percent, a pH-ier flow time of 48 Seconds ι arises After adjusting the pH to 19, this solution can be earthed with water. Like 'am ’, lacquer paints (binding 2: 1) were produced in a polyester solution (binding 2: 1) with a solids percentage; A mixture of 70 gester and 30 parts by weight of hexavalent derivative (HMM), 119 seconds show a deep drawability, an impact depth of> 5 mm, coatings, the binding agent of which consists of polyester and 20 parts by weight, a hardness of 126 seconds of 10, 6 mm and a 5 mm tentansprtlche: coating agent based on a binder and organic lo-) the additives that make the water and the binder or, if necessary, on a solvent-free basis l 1. Mixture ai communication media water soluble possibly also the as bin idcmii whose Weight percent aminoplasts and / ο low molecular weight, defined pre A. 50 to or de stages and B. 50 to 91% by weight of hydiroxyl groups containing carboxyl groups are linear Polyes ^ r from ethylene glycol, propanediol (1.2) and possibly other diols on the one hand ₍ On the other hand, aromatic and aliphatic dinic acids such as carbon next to Fabrics by Misc or their graduate with Mixed condenser * If necessary, the usual additional and auxiliary bags, with the binding agent also condensation of aminoplasts and / nedermolckularen, defined pre-linear polyesters or by nsation of the starting products of the aminoplast manufacture with the linear poly- “May have been made by it Inet that linear poijesters with> oil weights between 600 and 3000 estern herg: marked * middle are used, which have been prepared by esterification of mixtures I and II, wherein Mixture I. Ll to 70 to 30 mole percent of ethylene glycol and 1.2 consists of 30 to 70 mol percent of propanediol (1,2) and optionally up to 30 mol percent of the total amount of components 1.1 and 1.2 by one or more other aliphatic or cycloaliphatic diols, "1 to which the hydroxyl functions are replaced by 2 to 8 carbons atoms are separated and, if necessary, oxygen atoms can be in place of up to 2 of the carbon atoms, which in turn should be separated from each ^{other by at least 5 2 carbon atoms,} and mixture II Π.Ι. 91 to 33 mole percent from one or more * reren cycloaliphatic dicarboxylic acids in which the carboxy Ig groups are arranged in 1,2-eder 1,3-position, or aromatic Dicarboxylic acids and / or their derivatives and Π.2 to 9 to 67 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 characterized in that linear polyesters are used, for the preparation of which a mixture I has been used, which is 60 to 40 mol percent consists of component 1.1 and 40 to 60 mol percent of component 1.2. 3. Coating agent according to claim 1 and 2, characterized in that linear polyesters are used, for the preparation of which a mixture II has been used, the 75 to 50 mole percent of component ILl and 25 to 50 mole percent of component Π.2 4. Coating agent according to claim 1 to 3, characterized in that linear polyesters are used, for the preparation of which a mixture I has been used in the. up to 20 mol percent of the total amount of components 1.1 and Ϊ.2 by em or more others Diols have been replaced. . 5. Coating agent according to claim 1 to 4, characterized in that linear polyesters are used, for the production of which egg »mixture II has been used, up to 75 to 67 mole percent consists of component ILA and 25 to 33 mole percent of component Π.2.