DE2013097B2 - Coating agents - Google Patents

Description

The invention relates to liquid coating agents based on a mixture of binder and organic solvents or water and additives water-solubilizing the binder odei optionally also on a solvent-free basis, which acts as a binder

II. 1 to more than 70 to 100 mol percent of A 50 to 10 percent by weight aminoplasts and / or Butanediol (1,3) and 45 their low molecular weight defined precursors and

II. 2 to less than 30 to 0 mole percent of one or more other aliphatic or cycloahiphatic diols, in which the hydroxyl functions by 2 to 8 carbon atoms are separated and optionally up to 2 of the carbon atoms can be replaced by oxygen atoms, which in turn are replaced by at least 2 carbon atoms should be separated from each other and from the hydroxyl functions,

consists and mixture III

HI 1 to 90 to 30 mole percent of one or several aromatic or cycloahiphatic dicarboxylic acids and / or their Derivatives and

III 2 to 10 to 70 mol percent of one or more aliphatic dicarboxylic acids with 4 to 12 carbon atoms and / or their derivatives

consists

B 50 to 90 percent by weight of hydroxyl groups and carboxyl group-containing polyesters made from aliphatic diols and aliphatic polyols on the one hand and aromatic and aliphatic dicarboxylic acids on the other hand in addition to optionally usual auxiliaries

contain, wherein the binder can also have been produced by co-condensation of aminoplasts and / or their low molecular weight defined precursors with the polyesters or by co-condensation of the starting materials of the aminoplast production with the polyesters
It is known that so-called oil-free alkyd resins in combination with aminoplasts are suitable for the production of lacquer films. which contain 9 to 11 carbon atoms and their carbon chain in

«Position is branched to the carboxyl group Polyester should distinguish (H L Gerhardt and E E Parker, Ind Engng Chem 59, No. 8, 42 [1967])

Also in the USA patent 2 860 119 and in the publication by DL Edwards, DC F ι η η e y and PT vonBramerin Deutsche Farbenzeitschrift 20, 519 (1966), oil-free alkyd resins based on diols or polyols with a neopentyl structure are used described which, after crosslinking with aminoplasts, paint films with good chemical resistance, should result in high hardness and good flexibility, as our own comparative tests show such oil-free alkyd resins only with difficulty In addition, although they are hard, they are relatively less elastic (see comparative example 1)

From the USA patent 3 207 715 is still known that polyester from trimellitic anhydride, neopentyl glycol and adipic acid in combination with tetrakis (alkoxymethyl) benzoguanamines lacquer films result, the good chemical resistance and good The purpose of this patent specification is to have flexibility However, the values given show that the flexibility of this varnish film is comparative What is improved is that the absolute values are still there are very low.

In US Pat. No. 3,158,584, alkyd resins are made from a phthalic acid, a polyvalent one Alcohol and a dimer of an unsaturated aliphatic Monocarboxylic acid containing 14 to 22 carbon atoms, described in combination with aminoplasts result in lacquer films which are characterized by characterized by the combination of hardness and elasticity The varnish vapors produced in this way, however, have a strong tendency to yellow and are not sufficiently solvent-resistant

In US Pat. No. 2,460,186, polyesters made from 2-Ethylenhexanediol- (1,3) are used as plasticizers of exceptional value for the application tn Urea-formaldehyde or melamine-formaldehyde condensation products described The coatings obtained according to this α information are in part stretchable and impact-resistant, but too soft (see comparative example 2)

Also in the company publication »1,4-Cyclohexanedimethanol« of the Eastman Kodak Company of July 1965 describes oil-free alkyd resins made from Pelargonic acid, phthalic anhydride, pentaerythritol, neopentyl glycol and 1,4-bis (hydroxymethyl) cyclohexane are made and should be both hard and elastic, these polyesters should also meet not the expectations you have set, like your own Experiments show (see comparative example 3)

In the USA patent 3 338 743 wire enamels are based on polyesters and low Amounts of aminoplasts described With these lacquers is primarily a good temperature resistance Value placed information on the elasticity the coatings obtained from these wire enamels cannot be found in the patent

The USA patent 3 370 975 claims the Improvement of the adhesion of alkyd aminoplast resin systems on the respective substrates Adducts are selected as adhesion-improving additives Polymers that contain free hydroxyl groups and dicarboxylic anhydrides are used Production of these adducts in addition to copolymers from ζ B allyl alcohol and styrene, polyethers, polyvinyl alcohols, modified Polyvmy oxide resins also polyester used little information was given about the composition of this, as about use of alkyd resins

In the German Auslegeschnfi only water-soluble Embi ben, where also oil-free polyes

Chlorides and epetz, but polyesters are just as much the

1250 036 are used to make snow be used as a binder component ten m of the acid component only amounts of carbocyclic bivalent In addition, the pol} hol component contain very high proportions The stoving enamels described have hardness, but let their elasticity j Practical demands left a lot to be desired.

In the German exposition

solvent-free stoving enamels ζ ao aminoplasts are described, which are added plasticizers that aminoplast solution and solvent is distilled off

Suitable plasticizers are hydrc »5 plasticizers, such as ζ Β

However, they are also soft without hydroxyl lipids

101 667 are obtained on the basis of this with usual then the Is especially containing gexyl groups called zinusol,

Makers such as petroleum distillates or plasticizers are used Pulling agents produced by stoving only have low solvents Rings have poor chemical resistance on metals and d satisfactory mechanical properties From the German patent specification subsequently known that from the supervisory

German © 1108 667 described by the addition of a hard coating agent improves the coating properties but does not achieve this
From British Patent 81

dispersible coating agents known which besides Aminoplasts and optionally resins polyesters with molecular gc 800 and 1500 contain the polyesi at least 25 mole percent, before:

50 mole percent polyol with at least groups

Furthermore, the German script 1 669 104 describes lacquer polyester, wel Terephthalic acid in the acid component With regard to the alcohol component:

Indications made that by the

Selection of diols especially from L__ "

trains are obtained, describes this publication

at no stead

Contain polyester

subordinate

Carboxylic acids

ster m the alcohol

'olyole the whore

1 a good one

: about the ar> -

Conventional phthalate such over put coatings stability and security ruber also unifte 231 833 is white

Designed for cold-hardening, a ver-1 becomes thereby

179 are water

ubhchen alkyd densities between but contain more than; ns 3 hydroxyl

e Disclosure: he predominantly contains nents, there are no • inventive load-bearing

In the earlier patent application of the

German open

laying down 1 954 678 binders for coatings described, which consist of a polyester and an aminoplast In contrast to the previous one Invention is powdered and non-liquid products

composition the phase of the

it cannot be seen to what extent Zi and molecular weight have an influence Product also contain the products predominantly aminoplasts

In the older patent applications of the German Offenlegungsschften 1644 848 and 1794 375

the coating agent also made of modified 2 carbon atoms from each other and from the hy-aminoplasts and hydroxyl-containing polydroxyl functions are to be separated are suitable esters described As the only example ent- ζ Β ethylene glycol, propanediol (l, 2), propanediol (l, 3), can be taken, these are the butanediol (1,2), butanediol (2,3), butanediol (1,4), Use of branched polyesters with carbon-5 2,2-dimethylpropanediol- (1,3), hexanediol- (1,6), 2-ethylic acid-modified Aminoplasts The use of hexanediol- (l, 3), cyclohexanediol- (1,2), cyclovone Butanediol- (1,3) is not described hexanediol- (l, 4), l, 2-bis (hydroxymethyl) cyclohexane,

The invention is based on the object of producing 1,3-bis- (hydroxymethyl) -cyclohexane, 1,4-bis- (hydroxymethyl) in which high elasticity is achieved with methyl) -cyclohexane, x.8-bis- (hydroxymethyl ) - unite tri-large hardness and the moreover not io cyclo- [5,2, l, 0 ² , '] - decane, where χ for 3, 4 or 5 tend to yellow and stands opposite to aromatic ones, dietylene glycol, trietylene glycol, dipropylene- Solvent resistant are glycol or tripropylene glycol cycloahiphatic diols

Surprisingly, this object was achieved in its cis or trans form or as a gel solution that coating agents were found in which a mixture of both forms is used Use weights between 250 and 5000 are used, of ethylene glycol, propanediol (1,2) and / or 1,4-bisdie by esterification of mixtures I and III herge- (hydroxymethyl) -cyclohexane preferred
have been made, where mixture I As aromatic or cycloahiphatic dicarbon

acids are ζ B phthalic acid, isophthalic acid, hexa-

I 1 to 1 to 50 mol percent of one or more ao hydroterephthalic acid, tetrahydrophthalic acid, hexarene aliphatic polyols with 3 or 4 hydophthalic acid, hexahydroisophthalic acid and endroxyl groups and 3 to 6 carbon atoms of domethylene or endoethylene tetrahydrophthalic acid, and hexachloro-endomethylene-tetrahydrophthalic acid

or tetrabromophthalic acid suitable, the cyclo-

I 2 to 99 to 50 mol percent of a mixture II as aliphatic dicarboxylic acids in their trans- or cis of aliphatic and optionally cyclo- form or as a mixture of both forms of aliphatic diols can be used The use of dicarboxylic acids in which the carboxyl groups m 1,2- or consists, which in turn are arranged in the 1,3-position, in particular of phthalic

30 acidic, is preferred.

II 1 to more than 70 to 100 mole percent from butane. and especially succinic acid, glutaric acid, adipic acid,

Cork acid, sebacic acid, decanedicarboxylic acid or

II. 2 to less than 30 to 0 mol percent from a 2,2,4-Tnmethyladipinsaure But it can also or more other aliphatic or 35 unsaturated dicarboxylic acids, such as macycloahphatic diols, in which the hy- leinic acid, fumaric acid, itaconic acid or citracondroxyl functions through 2 to 8 carbon acids are used, but the use atoms are separated and optionally up to saturated aliphatic dicarboxylic acids with 4 to 2 of the carbon atoms can be replaced by oxygen atoms 6 carbon atoms, in particular adipic acid, which in turn are the only ones Ahphatic dicarboxylic acid preferred
at least 2 carbon atoms from each other and instead of the free dicarboxylic acids can also

their esters with short-chain alkanols are separated from the hydroxyl functions, ζ. Β dimethyl, should, diethyl or dipropyl ester, are used So

far the dicarboxylic acids can form anhydrides

consists, and mixture III 45 these can also be used, e.g. B hexahydrophthalic

acid anhydride, tetrahydrophthalic anhydride, succinic

III 1 to 90 to 30 mol percent of one or more anhydric anhydride, glutaric anhydride or maleic anhydride aromatic or cycloaliphatic di- acidic anhydride. Phthalic acid is preferably used and / or their derivatives, anhyd

Get 50 coatings with particularly good properties

III 2 to 10 to 70 mol percent of one or more when using polyesters with medium ren aliphatic dicarboxylic acids with 4 to molecular weights from 800 to 4000, in particular 12 carbon atoms and / or their den- from 800 to 3000, the predominantly hydroxyl groups fathers included, d. h with a molar excess

55 alcohol components (diols and polyols) produced

The properties of the coatings are made

further improves if one uses polyester

In the context of their preparation, a mixture I is used under the mean molecular weight of the present invention, the number average is that which is 10 to 30 mole percent from component I. 1 Molecular weights of the polyesters used are 60 and 90 to 70 mol percent from component 1.2 there is also a component III is preferred,

As polyols are ζ B glycerine, Tnmethylolathan, which 50 to 75 mol percent from III 1 and to Tnmethylolpropane and pentaerythritol suitably consists of 25 to 50 mol percent of III 2

As to be used in subordinate quantities The production of the polyester can after all Diols in which the hydroxyl functions by 2 to 65 known and customary processes, with or without S carbon atoms are separated and optionally a catalyst, with or without passing through an inert bis to 2 of the carbon atoms by oxygen atoms in the gas stream, as solution condensation, melting cones can be, which in turn by at least densation or azeotrope esterification, at temperature

doors up to 25O ⁰ C high carried out or, wherein the water liberated or released alkanols are continuously removed, the esterification proceeds almost quantitatively and may be monitored by determination of the hydroxyl and acid numbers The molecular weight of the polyester let over in a simple manner the Emsatzverhaltnis of alcohol component (diol and polyol) and Dicarbonsauie regulate this purpose, for the preparation of polyesters with predominantly hydroxyl groups on η mole of diol and m mole of polyol (n + m - 1) used mole dicarboxylic If, however, polyesters are prepared which contain predominantly carboxyl groups, the amount of dicarboxylic acid to be used is calculated according to the formula M = η + m (x - 1) + 1, in which M is the amount (in mol) of dicarboxylic acid that must be used when a polyester containing carboxyl groups is made of η mol Diol and m mol of a polyol containing χ hydroxyl groups is to be prepared Esterification conditions chosen so that the reaction is as complete as possible, d. h until the acid number is less than 5 mg KOH / g in batches which are used to produce polyesters containing hydroxyl groups Keep the alcohol component to dicarboxylic acid between the limit values mentioned. In these cases, care must be taken that the condensation is terminated in good time, ie when the desired molecular weight is reached

The esterification temperature is chosen so that the losses of highly volatile substances remain low, i.e. at least during the first period the esterification is esterified at a temperature below the boiling point of the lowest boiling starting substance.

When producing the polyester, it is important to note that both the molecular weight of the polyester and its composition influence the properties of the paint films produced from them have at higher Medium molecular weights are generally reduced the hardness of the paint film, while the Elasticity increases, on the other hand let go at lower molecular weights the flexibility of the paint film with a simultaneous increase in hardness according to similar Differences in the composition also have an effect of polyester made of · With a higher proportion of aliphatic dicarboxylic acids and larger The chain length of the aliphatic dicarboxylic acids increases the elasticity of the paint film, while its hardness is decreased The reverse is true with increasing The proportion of aromatic and / or cycloaliphatic dicarboxylic acids in the polyester makes the paint film harder and less flexible The diols exert a similar influence: with increasing chain length the open-chain diols and as the proportion of these diols in the polyester increases, the paint film becomes softer and more flexibly, however, diols with very short diols are also used in the production of the polyester and branched carbon chains or with cycloaliphatic ones Rings, the paint films produced from these polyesters usually become with increasing Percentage of these diols is harder and less elastic. Also the molar ratio of polyol to diol is dei for mechanical properties Paint films of importance. With decreasing mole The ratio of polyol to diol also decreases the hardness of the Films off while their elasticity is increased In the case of larger molar ratios, polyol is swept towards Diol reduces the flexibility of the paint film «and their hardness improved. If you know these rules it is possible without difficulty within the scope of the claimed range polyester with for the ever

ίο particular purpose of the e according to the invention

To select the optimal properties of the coating agent As suitable aminoplasts, the known

Reaction products of aldehydes, in particular Formaldehyde, nut several ammo or amido groups-bearing substances in question, such as ζ Β Melamine, urea, Ν, Ν'-ethylene oil, dicyan Diamid and Benzoguanamm are also suitable Mixtures of such products The aminoplasts, especially those with, are particularly suitable

ao alcohols modified ammoplasia

Because of the sometimes only limited tolerance These resinous products with the polyesters to be used according to the invention are preferred the low molecular weight, defined stages of Ann noplasts to be used with the invention Polyesters can be mixed in practically unlimited ways, Such defined precursors of ammo plastics are ζ B Dimethylomaarnstc ff, tetramethylol benzoguanamm, Tnmethylolmelam η or Hexame thylolmelamin, which also in part; or completely ether form, ζ B as Dimethoj ymethylurea, Tetrakis (methoxymethyl) benzogua iamm, Tetrakis (ethoxymethyi) -benzoguanamine or polyether des Hexamethylolmelamms, such as Pentakis- (methoxymethyl) -mono- (hydroxymethyl) -melamiQ, Hexakis (meth oxymethyl) melamine or Hexakii (butoxymethyl) melamine, can be used

If necessary, it is also possible to ensure miscibility between the resin types _; To improve 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 Ge

total amount of solvent) to high-boiling polar ones Loose for both resins, such as ethyl glycol acetate, butyl glycol or <

ζ B ethyl glycol, ir cyclohexanone,

adds or preferably polyester and ammo plast reacts with one another in a known manner in substance in solution, where has to ensure that the reaction is not linked to crosslinking As this progresses, ζ B by warming the mixture or the common solution of the two resins, optionally ir catalyst, such as ζ B organic or minerali see acids, the polyesters to be used according to the invention are achieved even before or during the production of the Ammo plast resins from ζ B urea, beizoguanamine or Melamine and aldehydes common alcohols for modifying the so formed plasticized aminoplast resins with :: uuse the Methods of making such] Amm-aldehyde resins for both Io as well as for aqueous paint systems are known, a large number of suitable working instructions are in the To find literature (cf.

or, preferably, one is approaching it

brief er

Presence of one

It's mog too

ζ to add where I am, in addition

ger plasticized «* containing solvents

ipiel H ο u b e η

409543/340

9 10

W e y 1, Methods of Organic Chemistry, 4. Can be used without a medium. Such mixtures are

lage, Vol. 14/2, S 319 ff, Georg-Thieme-Verlag, Stuttgart at room temperature or, if appropriate, included

gart, 1963 or Ulimann's Encyklopadie der tech- Temperatures up to 7O ⁰ C (to reduce the

Chemicals, 3rd edition, Vol. 3, S 475 ff, Urban processing viscosity) in brush, roller or dipping

& Schwarzenberg, Munich, 1953) 5 method based on the objects to be coated

For combination with the entered according to the invention, the wet layer thickness should be used to offset Polyesters are available for a large number of commercial avoidance of blistering not being chosen too high higher aminoplasts or whose defined precursors are. It is also possible to have the processing proprietary Grouting of the shafts of solvent-free coating agents

Although very low molecular weight polyesters in combination by adding small amounts (up to about 10 Genation with the low molecular weight, defined weight percent, based on the total binder) levels of aminoplasts even without solvents, i.e. the viscosity of such can be used to lower the production of the systems and the tendency for bubble coatings usually first to suppress polyester and amino formation

plast or its defined preliminary stages in the usual 15 The lacquers can use the usual additional and auxiliary

Paint solvents, such as propanol, contain iso-materials, such as pigments, leveling agents

Propanol, butanol, ethyl acetate, butyl acetate, ethyl agents and additional other binders, such as ζ Β.

glycol, ethyl glycol acetate, butyl glycol, methyl ethyl epoxy resins and hydroxyl group containing Sihcon-

ketone, methylsobutyl ketone, cyclohexanone, trichloro resins

ethylene or mixtures of different such 20 The varnish obtained is applied and Tem-solvent, dissolved It is of course also temperatures between 100 and 25O ⁰ C baked. The crosslinking reactions which are possible and recommendable for economic reasons are worthwhile, more or less large amounts less polar catalytically accelerated by acids acidic substances are added to the varnish when turning Polyester and wetting are greatly accelerated As the ammosate used is more compatible with acidic acid, plastics that dry at room temperature can also be selected; it can often produce a proportion of coatings, even when using aqueous up to 80% and more in the solvent mixture, lacquer solutions which, as described above, can be used by new are obtained, the crosslinking with water-resistant aminoplasts is achieved by adding

When using polyesters with a high acid number, 0.5% p-toluenesulfonic acid (based on the

i.e. with polyesters, which accelerate a larger number of total binders

Having non-esterified carboxyl groups, it is also possible by reacting a low-acid polyester

Of course, it is also possible to use aqueous solutions with an anhydride of a relatively strongly acidic dicar-

This can be done according to the well-known and bonsaure, ζ B maleic anhydride, one can use the

usual methods are carried out (cf. for example W A 40 subsequently increasing the acid number of the polyester and so on

Riese, "Loser-free paint systems", Curt R Vm- even without the addition of strongly acidic substances

centz-Verlag, Hanover 1967, S 432 ff), whereby in the stoving temperatures lower the increase in

Usually all or part of the carboxyl groups of a polyester is usually in the acid number

are neutralized with amines and, if necessary, melt carried out, including the melt of the poly

The selected amount of acid anhydride was also added to the water-miscible solvent 45 esters

are also used, which will serve as a loosening agent, whereupon after complete dissolution of the anhydride

It goes without saying in the preparation of the batch up to the complete addition of the anhydride

aqueous coating solutions required in Los water at temperatures up to 150 ⁰ C. It is heated

borrowed aminoplasts to use, the low molecular weight, however, there are no difficulties, the same

lar, defined precursors of aminoplasts are also reactions in the solution of the polyester among the

to carry out the reaction conditions particularly suitable for this purpose, it

However, the weight ratio of polyester to aminoplast must be ensured that the solution

can between 50 · 50 and 90:10, preferably medium does not contain any functional groups below

between 65.35 and 85:15, vary; the same for the reaction conditions mentioned

respective application of the lacquers optimal 55 can react to the acid anhydride

The ratio can easily be obtained with a few preliminary tests. The coatings produced according to the invention

In doing so, it must be taken into account that there are often a wealth of good properties.

by increasing the proportion of aminoplast the hardness is glossy, easy to pigment and yellowing

the paint films are increased and their elasticity is constantly reduced. The coatings are subject to heat aging

is, during the aminoplast arrival subjected at lowering 60 of 72 hours at 100 ⁰ C, so is not

partly the hardness decreases and the flexibility increases visible yellowing noticeable, also a warm

The Gesamtbmdemittel content of the coatings may vary aging of 72 hours at 15O ⁰ C, the erfinnach use in the usual limits dungsgemaßen over the course of a vergilbungsbestandig. The coatings are resistant to polyesters containing solution groups, ie those with average molecular weights such as xylene, benzene-benzene mixtures, esters, and ketones. They also have good molecular weights In combination with low molecular weight, acid and alkali resistance, for salt spray-defined precursors of aminoplasts also solution searches, tropical tests and tests in the Weatherometer

they show a good anti-corrosive effect and Weather resistance

The most outstanding property of the invention produced coatings is their great Elasticity at high hardness, even when overburned preserved

The elongation behavior of coatings is becoming common daduich described that you can do the Erichsea cupping test (according to DIN 53156) and the deepening of the lacquered as a measure of the elasticity Sheet metal in Milhmetei indicates where the paint layer starts to tear Essential to this test method it is that the deformation of the coating takes place slowly (feed 0.2 mm / sec)

The so-called impact depth measurement provides an indication of the behavior of coatings in the event of sudden deformation. This measurement can be carried out, for example, with the impact depth measurement device 226 / D from Enchsen, Hemer-Sundwig. With this device, a hemisphere with a radius of 10 mm is suddenly imprinted into the sheet metal from the back of the paintwork by a falling weight The lacquer layer begins to tear (the values given in the examples were obtained in this way. In some examples, the value> 5mm is given because the device described does not allow a larger deep-drawing with the 1 mm thick deep-drawn sheets usually used for testing)

As with the description of the state of the art was carried out and proven by comparative tests are already coatings made of polyesters and Aminoplasts known that are stretchable and also withstand impact stress These coatings However, they have very little hardness (according to DIN 53 157). On the other hand, coatings are of high hardness known, but they are only slightly or not elastic or they are elastic, but a number of others Disadvantages such as a tendency to yellowing and poor resistance to solvents In contrast, the coatings obtained according to the invention have both high and high elasticity great hardship, but not the disadvantages mentioned.

This property profile opens up the coatings Versatile application In addition to painting individual parts that are exposed to impact stress smd, the main thing is the painting of materials into consideration, the subsequent - z. B by punching - be deformed

The polyesters used in accordance with the invention are either of low viscosity as such or result in low viscosity solutions therefore process paints with high solids content, which can be used to save work steps.

The following examples serve to further illustrate the invention

Polyester manufacturing

360 g of butanediol (1,3) (4 mol), 92 g of glycerol (1 mol), 62 g of ethylene glycol (1 mol), 518 g of phthalic anhydride (3.5 mol) and 219 g of adipic acid (1.5 mol) are included stirring and passing a gentle stream of nitrogen within 8 hours of 14O ⁰ C was slowly heated to 200 ⁰ C. After 11 hours at

The resulting polyester has 200 ^{° C.}

of 3.0 mg KOH / g and a hydrox

of 3.0 mg KOH / g and one

111.6 mg KOH / g on night

Melt to 140 ⁰ C is the poly «

a mixture of 6 parts by weight of xylene,

Butanol and 2 parts by weight of AtI ylglykolacetat dissolved to a 60% solution

an acid number of 111.6 m Iffydroxyl number from cooling the ster in a Ge-2 Parts by weight

to the

Increase the acid number a ©

mt

To melt a polyester
number will be 1.8% maleic anhydride
»5 the pure polyester) given Na | (
put anhydride is completely dissolved,
120 ⁰ C heated, whereby the acid number
is increased by 10.1 mg KOH / g.

low acidity (based on chdem das trains 1 hour on the polyester

Making a la

The solutions of the polyester in suitable solution medium, usually a mixture of xylene and emerr polar solvents, are used with

55% solution of a melamine-Fbrmaldehyd-Kon densates in xylene-butanol mixture

a commercial hexamethylolmelamine derivative im desired solids ratio

A polyester to melamine resin ratio of 7 3 would be, for example, 117
Solution of the polyester with 54.5 g de

r mentioned melamine resin solution mixed, should polyester and melamine-formaldehyde condensate not be contractual with each other, the Gemii
- for low-acid polyesters below

p-Toluenesulfonic acid, based on the total amount of polyester and aminoplast -, ID ^{heated to 50 to 100 °} C. for up to 60 minutes

Polyester

one more for sale

(1 1) or mil

rmischt um eic

g of a 60%

ch of the solutions addition of 0.5 %

Solvent-free for production
the low-viscosity polyester and a

; r lacquers are commercially available hexamethylolmelamine derivatives mixed together in the desired solids content

Manufacture of a paint color

v is a clear coat of 2 1 with

b:; w

For the production of a paint color

in the binder to pigment behavior

TiO ₂ pigmented

Manufacture and testing of the

The clear coat is used for testing

on test panels and glass plates

branded to humiliate the

door is varnishes made using '.
low acid number was produced 1,

sulfonic acid (based on the

added The layer thickness of the

Check is carried out, amounts to m all '.

The hardness test is carried out in accordance with
Test of elasticity according to the above

low methods. The solvent resistance

the cover is made with the hooves of the

written testes checked the au]

Burned-in paint film is used
15 minutes in xylene immersed in NaIc

will take the swelling and

Assessment of the film's sensitivity to scratching,

The following grading system was used

Covers

the lacquer color applied and fired tempera polyesters , 0.5% p-toluene G ^ samtbmdemittel) on which the 40 to 60 μ. PIN 53 157, the snowing

FiI ne _:
Beis Jielen

below a glass plate room temperature ch the out Fmgernagel, where fol is

Swelling

1 = core swelling,

2 = weak, just recognizable in accusation

Swelling,

3 = clearly recognizable swelling,

4 = strong swelling,

5 = very strong swelling.

Scratch resistance

1 = absolutely scratch-resistant,

2 = film is partially damaged on the surface,

3 = film surface is badly damaged,

4 = film damage up to the glass plate,

5 = film can be wiped off

The evaluation is set in a double grade (e.g. 1/1), where the first mark indicates the swelling and the second mark the scratch resistance.

Examples 1 to 22 are compiled in Table 1, Table 2 also contains the type of melamine resin used the test values of the coatings resulting from the Comparative Examples 1 to 3 described below Polyesters were made

Comparative example 1

(Alkyd resin No. 8531 - 69 from Deutsche Farbenzeitschrift 20, 519 [1966])

A mixture of 257 g of methylol propane, 351 g of neopentyl glycol, 498 g of isophthalic acid, 292 g of adipic acid and 15 ml of xylene was described in strict compliance with that described on page 521 of the cited literature reference Esterified reaction conditions when an acid number of 28 mg KOH / g was reached the approach immediately cooled with the help of ice, whereby to accelerate the cooling, an additional 500 g of a mixture of 90 parts of xylene and 10 parts Butanol was carefully added to the reflux cooler Reaction conditions and those for rapid cooling Actions must be taken so that the approach does not - like failed attempts showed - prematurely crosslinked The solution obtained was with a further 312 g of said xylene-butanol mixture diluted to make a 60% resin solution obtain.

Comparative example 2

(Example 4 from USA patent 2 460 186)
148 g of phthalic anhydride, 202 g of sebacic acid, 278 g of 2-ethylhexanediol (l, 3), 28 g of glycerol and 110 ml of xylene are slowly ^{warmed to 230 °} C. in 11.5 hours and the water formed is separated off using a water separator esterification is abdestilhert the solvent slowly and held for 3 hours at 230 ⁰ C.

Comparative example 3

(Alkyd resin from the company publication »1,4-Cyclohexanedimethanol« Eastman Kodak Company dated

Juh 1965)

A polyester was made under the conditions specified on page 11 of the company publication mentioned 160 g pelargonic acid, 300.6 g phthalic anhydride, 70.0 g neopentyl glycol, 95.6 g 1,4-bis (hydroxymethyl) cyclohexane and 133.2 g of pentaerythritol prepared. The polyester obtained had an acid number of 7.6 mg KOH / g and was diluted with xylene to a 60% solution

Tabel

1 polyester Mitt
leres Weight
relationship Type of V _a * _Q 1 _w Burn-in Hardness
after Deep- Impact Solution
with ti »! at the end mole Polyester too melamine JVoIaiy- conditional DIN pulling
able to- deepening iniiici- game kular
weight Melamine resin
ZuTiO ₂ resin sstor worked 53157 Kell DSSt 0.Π "·
age No [MoI] [sec] Helen
DIN
53156 [mm] 2 3BG *) 807 70 30 0 HMM *) 0.5% pTS *) 140730 ' 212 [mm] 3 1/1 1 PPE *) 70 30 50 HMM 0.5% pTS 140730 ' 173 7.6 2 to 3 1/1 2 BSA *) 6.5 IGIy 3 3BG 887 70 30 0 HMM 0.5% pTS 140730 ' 180 5 1/1 1.5 PSA 70:30:50 HMM 0.5% pTS 140730 ' 135 7.9 4th 1/1 1.5 AS *) 7.8 IGIy 4th 4BG 1430 70.30 0 HMM 0.5% pTS 140730 ' 167 5 1/1 IAG *)
3.5 PPE
1.5AS 70 30-50 HMM 0.5% pTS I4O73O ' 124 8.3 2 to 3 1/1 IGIy 7.3 4BG IPG- ") 1610 70-30-0 HMM 0.5% pTS 140730 ' 185 4th 1/1 3.5 PPE 70:30 50 HMM 0.5% pTS 140730 ' 124 8.2 4th 1/1 1.5AS 7.9 IGIy

15th

16

Table 1 (continued)

example

polyester
the end

[Mole]

Middle Molecular weight

Weight behavior

Polyester to melamine

ResinzuTiOj

Type of

melamine

resin

catalyst

A burning condition

Hardness
after
DIN

53157

[sec]

Deep drawability according to DIN 53156

[mm]

Impact depression

[mm]

Solution medium-strength

5BG 1785 3PSA 3AS 2GIy 6BG 2020 4.5 PPE 1.5AS IGIy HBG 2940 9PSA 2AS IGIy 7BG 2980 2PG 6PSA 4AS 2GIy 4BG 1560 1ÄG 3IPS *) 2AS IGIy 8BG 2610 2 AG 7PSA 3AS IGIy 2.5BG 966 0.5 CHDM *) IGIy 1.5 PSA 1.5AS 4.5BG 2160 1.5 CHDM IGIy 4.2 PSA 1.8AS 4.5BG 2030 1.5 CHDM IGIy 4IPS 2AS 8BG 2950 2 CHDM IGIy 8PSA 2AS

70 30 0 70.30: 50

70.30. 0 70.30 50 70: 30.50 70 30 50

70 30 0 70.30-50

70-30. 0

70 30: 0 70:30:50

70:30: 0

70:30: 0 70: 30.50

70:30 0 70:30:50

70.30: 0 70.30: 50

70:30: 0

HMM
HMM 0.5% pTS
0.5% pTS 140730 '
140730 ' HMM
HMM
K *)
K 0.5% pTS
0.5% pTS
0.5% pTS
1.8% MSA
MSA ^H ) 140730 '
140730 '
140730 '
140730 ' HMM
HMM 0.5% pTS
0.5% pTS 140730 '
140730 ' HMM 0.5% pTS 140730 ' HMM
HMM 0.5% pTS
0.5% pTS 140730 '
140730 ' HMM 0.5% pTS 160730 ' HMM
HMM 0.5% pTS
0.5% pTS 140730 '
140730 ' HMM
HMM 0.5% pTS
0.5% pTS 140730 '
140730 ' HMM
HMM 0.5% pTS
0.5% pTS 140730 '
140730 ' HMM [>, 5% pTS 140730 '

101
111

140
139
120
104

130
124

145

169
133

122

191
155

186
171

7.9 6.6

9.4 7.9 5.9 5.8

9.6 8.9

8.4

8.8 8.6

8.4

7.6 6.5

8.4 8.1

8.0 8.5

8.8

5 ¹ 4 to

> 5

5 3

> 5> 5

> 5

> 5

4 4

4 to

5> 5

4 to

2/1 2/1

1/1 1/1 1/1 1/1

2/1 2/1

1/1

1/1 1/1

1/1

1/1 1/1

1/1 1/1

1/1 1/1

1/1

409543/340

polyester Mitt
leres Weight
cautious Tabel I (continued) A-
hrf * n η a Hardness
after Deep- Impact Solution
mid- the end Molecu
lar
weight Polyester too
Melamm
resin to TiO ₃ conditional
worked DIN
53157 pulling
able to-
ίτ * »ιί deepening persistent
digfceit at [Mole] Type of [sec] after
DIN
53156 [mm] game
No 5BG 1655 70 30. 0 Melamm
resin sator 160730 ' 127 [mm] 5 1/1 I DM 7.8 15th IGIy HMM 0.5% pTS 2PSA 4BSA 3BG 1230 70 30 · 0 140730 ' 204 4th 1/1 I DM 70 30 50 140730 ' 146 7.8 3 to 4 1/1 16 IGIy HMM 0.5% pTS 6.7 2.5 PPE HMM 0.5% pTS 1.5AS 6BG
4 5 1480 70 30 50 140730 ' 113 5 2/2 HHPSA *) 7.8 17th 1.5AS HMM 0.5% pTS IGIy 4BG 1290 80-20 50 14071h 146 > 5 1/1 1ÄG 80 20 50 I6O73O ' 163 9.1 5 1/1 18 **) 5PSA HMM 0.5% pTS 7.7 2AS HMM 0.5% pTS IGIy 2.5BG 1050 80: 20 · 0 14071h 179 5 1.1 0.5 80 20:50 14071h 165 8.4 4 to 5 1/1 CHDM HMM 0.5% pTS 7.5 3.5 PPE 80-20: 0 HMM 0.5% pTS I6O73O ' 175 3 1/1 1.5AS 80-20.50 I6O73O ' 183 7.5 2 to 3 1/1 IGIy 70 30-0 HMM 0.5% pTS I8O73O ' 176 5.8 > 5 1/1 3BG 1037 80 20. 0 HMM 0.5% pTS 14071h 124 9.5 5 1/1 3.5 PPE 80 20-50 HMM 14071h 161 8.2 4 to 5 1/1 20 ***) 1.5AS 80.20 0 HMM 0.5% pTS 16071h 122 7.6 4th 1/1 IGIy 70-30. 0 HMM 0.5% pTS I8O73O ' 128 7.5 > 5 1/1 4BG 1470 80-20 0 HMM 0.5% pTS 14071h 159 9.6 > 5 2/2 IPG 80-20 50 HMM 14071h 125 10.0 > 5 1/1 21 ***) 5PSA 80-20-50 HMM 0.5% pTS I6O73O ' 149 8.4 4 to 5 1/1 2AS 80 20 50 HMM 0.5% pTS I6O73O ' 105 9.6 > 5 2/2 IGIy HMM 0.5% pTS 9.3 2BG 530 70 30-0 HMM 140730 ' 126 4th 1/1 0.7 PSA 70 30:50 140730 ' 122 7.8 3 1/1 22nd 1,3AS HMM 0.5% pTS 7.6 IGIy HMM 0.5% pTS solution 70:30. 0 I6O73O ' 114 2 to 3 1/1 belt-free 6.8 HMM 0.5% pTS

*) Abbreviations

BG = butanediol (1,3) PSA = phthalic anhydride BSA = succinic anhydride GIy = glycerine

HMM = hexamethylol melamine indenate pTS = p-toluenesulfonic acid AS = adipic acid AG = ethylene glycol PG = propanediol- (1,2)

K = melamine-formaldehyde condensate MSA = maleic anhydride IPS = isophthalic acid

CHDM = 1. ^ bis-hydroxymethyl-cyclohexane HHPSA = hexahydrophthalic anhydride

**) This example relates to a water-soluble coating agent which was obtained as follows
The polyester with an acid number of 77.0 mg KOH / g and a hydroxyl number of 53.0 mg KOH / g is ^{neutralized at a temperature between 70 and 80 0} C with the calculated amount of Tnathylamm and diluted with isopropanol to an 80 percent solution, which is adjusted to a solids content of 50 percent by weight with water. This solution is mixed with a commercially available melamine-formaldehyde condensate in the specified solids content and again adjusted to a solids content of 50 percent by weight with water

** ♦) This example concerns a water-soluble coating agent, which was obtained according to note **)

Table 2

Ver
equal
example
No Weight
behavior
Polyester too
Melamine tararz too Melamine-
resin Kataly
sator Burn-in
conditions Hard after
DIN
53 157 Deep drawing
capability
according to DIN
53156 Blow
deep
[mm] I. <1 Solution
middle-
resistant-
speed TiO ₂ [sec] [mm] 2 1 70 30 · 0 K *) 0.5% pTS *) 150730 ' 216 5.1 1/1 70-30 0 HMM *) 0.5% pTS 150730 ' 217 5.1 <1 ^; 2/2 70: 30: 100 K - 150730 ' 185 1.8 Ibisj2 1/1 70 30,100 HMM - 15O ° / 3O ' 173 6.8 > 5 2/2 2 70.30. 0 HMM 0.5% pTS 130730 ' 28 9.2 > 5 4/4 70:30 0 K 0.5% pTS 130730 ' 24 8.3 <1 5/4 3 70 30 · 0 K 130730 ' 177 1.5 <1 2/2 70:30 0 K 0.5% pTS 130730 ' 177 1.5 <1 2/1 70:30 0 HMM 0.5% pTS 130730 ' 178 2.5 <1 2/1 70-30. 40 K - 150730 ' 109 1.8 <1 2/3 70 30 40 HMM - 150730 ' 105 6.0 2/3

*) Abbreviations

K = Melanun-formaldehyde condensate
HMM = hexamethylol melamine indenate
pTS = p-toluenesulfonic acid

Claims (7)

Claims 1. Liquid coating agents based on a mixture of binders and organic Solvents or water and the binder water-solubilizing additives or optionally also on a solvent-free basis that acts as a binder IO A 50 to 10 percent by weight aminoplasts and / or their low molecular weight defined precursors and B 50 to 90 percent by weight of hydroxyl-containing and carboxyl-containing polyesters from aliphatic diols and aliphatic polyols on the one hand and aromatic and aliphatic dicarboxylic acids, on the other hand, in addition to optionally customary auxiliaries contain, the binder also by co-condensation of aminoplasts and / or their low molecular weight defined precursors with the polyesters or by mixed condensation as the starting products of the aminoplast production may have been made with the polyesters, characterized in that polyesters with average molecular weights between 250 and 5000 are used, which have been prepared by esterification of mixtures I and III are, the mixture I I 1 to 1 to 50 mol percent of one or more aliphatic polyols with 3 or 4 hydroxyl groups and 3 to 6 carbon atoms and I 2 to 99 to 50 mol percent of a mixture II of aliphatic and optionally cycloahphatic diols consists, in turn 2 coating agents according to claim 1, characterized in that polyesters are used, a mixture I has been used for the preparation of which 10 to 30 mol percent of component I 1 and 90 to 70 mol percent of component I. 2 3 Coating agents according to Claims 1 and 2, characterized in that polyester is used only butanediol- (1,3) have been used for their production as component II is 4 coating agent according to claim 1 to 3, characterized in that polyester with average Molecular weights between 800 and 4000 can be used 5. Coating agent according to claim 1 to 3, characterized in that polyester with average Molecular weights between 800 and 3000 can be used. 6 Coating agents according to Claims 1 to 3, characterized in that predominantly hydroxyl groups containing polyesters with average molecular weights between 250 and 800 in combination with low molecular weight, defined precursors of aminoplasts m solvent-free or low-solvent form can be used 7 coating agent according to claim 6, characterized in that the coating agent up to 10 percent by weight of solvent, based on the total binder