DE2025173B2 - Coating compound in stock - Google Patents

Description

This invention relates to a shelf stable coating composition in a package for the manufacture of stretchable coatings made from a reaction product containing urethane groups, an aminoplast, a organic solvents and optionally customary additives. The invention also includes the use this coating composition for coating rubber-like elastic substrates.

Recent developments in the technology of producing coatings have resulted in coatings which are suitable for application to difficult-to-coat substrates of various types and which have a number of different properties. Coatings are obtained which have an excellent appearance and excellent durability and which are stable under severe environmental conditions. The coatings to which more stringent requirements are placed include those of vehicles, for example automobiles, which must retain their good appearance over a long period of time even under the action of the weather and under various other forms of wear.

Interest in use has recently turned from guninii-like, elastic fabrics for objects that are subject to mechanical shock resp. Such as shock absorbers and molded parts of automobiles, protruding corners are exposed to shock loads and surfaces of industrial machines, floor boards and other parts of doors and house entrances The use of these substances gives increased protection against permanent damage in the material structure, however, in order to give the objects a desired appearance, their surface must be coated with provided with a decorative protective coating, which can also be damaged during use. the Coatings of the more common types, including those previously stretchable on rubber and the like Objects have been used, however

JO does not have the required combination of properties on. These properties are:

1. Extensibility: This property is necessary so that the advantages of the elastic or resilient layer carrier can be fully effective,

J5 without affecting the uniform surface of the

Coating is damaged.

2. Tensile Strength: A high level of tensile strength is necessary to prevent the film from falling into the Use tears.

3. Package stability: For the purpose of easy handling in use, the liquid Coating mixture can be kept for a long time under given conditions without that in it resin may gel or depolymerize.

4. Persistence of the film: certain coatings that are stretchable and have a relatively high tensile strength lose these properties with aging and especially when the coating demolishes Sunlight, weather and similar influences is exposed.

Impact resistance: The coating must have an impact resistance at different temperatures, which correspond to temperatures as they occur in extreme weather conditions, i.e. temperatures between -29 ° C and +49 ⁰ C.

6. Adhesion: The coating must have the ability to be sufficiently strong on the various substrates to adhere to which it is applied, e.g. B.

bü stretchable materials, such as foams, rubber

and the like, and metals such as mild steel. In addition, the coatings must be used as intermediate layers Sufficiently high adhesive strength to other coating layers and to various types of

have high primers / primers.

7. Resistance to chemicals and moisture: These properties relate to resistance the coatings against saponification under the

Exposure to acids and alkalis, their resistance to various solvents and their resistance to an atmosphere of high humidity and great heat.
8. Resistance to cracking in the temperature-humidity cycle: This property is important when the coating is exposed to rapid changes in temperature and humidity such as that which automobiles can experience while driving or during storage. This property is tested by exposing the article coated with the coating alternately to the effects of high temperatures and high humidity and low temperatures and low humidity.
Other properties which are important for the usability of the coating mixtures from a commercial point of view relate to their sprayability at suitable solids contents, their non-toxicity and their low sensitivity to moisture.

It is very difficult to achieve the above properties in their entirety because one or several of the desired properties in most cases the use of substances and preparations make necessary, which usually cause a deterioration in the other properties desired. Coating compositions based on polyurethane resins are known and in numerous publications described. DT-PS 10 90 449 shows coating compositions that act as a film former, the reaction product of 4,4'-methylene-bis (cyclohexyl isocyanate) and an alkyd resin. The alkyd resin is said to be condensation a polybasic acid or its anhydride with a polyhydric alcohol and a fatty acid getting produced. These reaction products can be mixed with urea-formaldehyde resins or Melanin-formaldehyde resins are used.

The GB-PS 11 28 943 relates to the production of a polyurethane product, which in combination with a Aminoplast can be used as a coating mass. For the manufacture of the polyurethane product is a polyisocyanate with an alkyd resin from a phthalic acid, a dimer of an unsaturated aliphatic Monocarboxylic acid and one or more glycols unset.

In US-PS 32 42 230 are mixtures of water-soluble polyurethanes and phenolic and amino resins described. The water-soluble polyurethanes are water-soluble reaction products of Polyalkylene ether glycols and a diisocyanate.

In FR-PS 15 44 042 coating compositions are described that a polyurethane based on a Contain polyether polyol and an aminoplast.

It has now been found that compositions of certain slightly crosslinked urethane groups Reaction products of a polyisocyanate and a compound with several hydroxyl groups, an aminoplast, an organic solvent and, if appropriate, customary additives in one package Forming coating compositions with excellent storage stability and becoming coatings of high extensibility and tensile strength to process.

The object of this invention is therefore a storage-stable coating composition in a package the end

a) a urethane-containing reaction product of a polyisocyanate and a polyfunctional one Link,

b) an aminoplast,

c) an organic solvent and optionally

d) usual additives,

characterized in that it is an ungelled urethane reaction product containing hydroxy groups contains an organic polyisocyanate and an organic material with several hydroxyl groups, a major proportion of this material being a polyester polyol made from

(a) an alcohol component having an average functionality of at least about 1.9 and

(b) an acid component has been prepared consisting essentially of one or more carboxylic acids or their anhydrides with 2 to 14

Consists of carbon atoms in the molecule and has an average functionality of at least 1.9, wherein the alcohol component and the acid component a total of no more than about 1 Gram-moles of compounds with a functionality of 3 or more per 500 g of the alcohol component plus Contain acid component.

It is surprising that these coating compositions give crosslinked, thermoset coatings in spite of them are storable in a packaging. The ones from the Coatings produced according to the invention have the properties described in the introduction to a satisfactory extent and in a combination that cannot be achieved with known coating compositions

JO has been.

The coating compositions according to the invention can be applied to practically any solid substrate will. Particularly suitable are rubber-like, elastic substrates or carriers, such as polyurethane and Polyethylene foams, natural and synthetic rubber, rubber foam and various elastomers Plastics. They can also be particularly useful on other substrates such as mild steel and aluminum be used.

The coating compositions according to the invention contain an isoeyanate-modified, hydroxyl-containing resin obtained by using an organic material several hydroxyl groups, a major proportion of which is an essentially linear polyester polyol, reacts with a polyisocyanate. To produce the coating compositions according to the invention, the isocyanate-modified one is used Resin mixed with an aminoplast resin and the other components.

The alcohol component of the polyester polyol used must have an average functionality of at least about 1.9, and in most cases consists essentially of one or more Diols. You can also use triols or higher polyols, since a certain branching is desired, however, the polyester should not be highly branched. You can also use a small amount of a monoalcohol add especially when larger amounts of higher polyols are used.

bo If in certain cases polyols with a very high Molecular weight are used, these can largely or entirely consist of compounds with a Functionality of more than 2 exist.

Diols of the kind commonly used for the

hl manufacture the polyester used are the Alkylene glycols such as ethylene glycol, propylene glycol. Butylene glycol and neopentyl glycol, and other glycols, such as hydrogenated bisphenol A, cyclohexane dimethanol,

Caprolactone diol (the reaction product of caprolactone and ethylene glycol), hydroxyalkylated bisphenols, Polyether glycols such as poly (oxytetramethylene) glycol and the like of different types and, as said, polyols with a higher functionality are also used will. Examples of polyols of this type are trimethylolpropane, trimethylolethane and pentacrithritol and the like and furthermore polyols of higher! Molecular weight, such as that obtained by the oxalhylation of Low molecular weight polyols are obtained, called. An example of such a polyol with The higher molecular weight is the reaction product of 20 moles of ethylene oxide and 1 mole of trimethylolpropane.

The acid component of the polyester consists essentially of carboxylic acids or anhydrides with 2 up to 14 carbon atoms per molecule. The acids have an average functionality of at least about 1.9. The acid component contains in most cases at least about 75 mol% or dicarboxylic acids their anhydrides. The funklionalilä! the acid component is based on considerations similar to those in Relationship with the alcohol component were decisive, with the overall functionality of the System is to be taken into account.

Examples of acids that can be used are phthalic acid, isophthalic acid and terephthalic acid. Tetrahydrophthalic acid, Hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, malic acid, glutaric acid, hexachlorheplendicarboxylic acid, Telrachlorophthalic acid and other dicarboxylic acids of various kinds. The polyesters may contain minor amounts of a monobasic acid such as benzoic acid. You can also get higher Use polycarboxylic acids such as trimellitic acid and tricarballyic acid. Where acids are mentioned above, can of course also use the anhydrides of these acids, insofar as they form anhydrides, instead of the Acids are used. The polyester preferably contains, at least as part of the acid component, an aliphatic dicarboxylic acid.

The polyester is produced by known processes, the reaction conditions and the Ratio of reactants can be chosen so that a product with residual hydroxyl groups arises. The number of hydroxyl groups contained in the product can vary, but the The hydroxyl number can usually be at least about 30, preferably more than 80.

Mixtures of polyester polyols can also be used as organic material with several hydroxyl groups be used with polyether polyols. Such polyether polyols have a hydroxy equivalent of at least about 100 and contain a total of no more than about 1 gram of volume with a Functionality of 3 or more per 500 g of the polyether polyol. You can also use smaller quantities other hydroxyl-containing compounds such as low molecular weight polyols, especially diols such as 1,4-butanediol or Neopentyl glycol monohydric alcohols and polyfunctional Compounds with one or more hydroxyl groups such as ethanolamine can be used. Suitable are also compounds that contain other active, hydrogen-containing groups, such as water and polyfunctional amines. Examples are; Isophoronediamine, p-mcnthandiamine, propylenediamine, Hexamethylenediamine, diethylenetriamine, triethylenetetramine. Diethanolamine et al.

As an organic polyisocyanate, the one containing the hydroxyl groups Material is implemented, map can basically use any polyisocyanate, for example Hydrocarbon polyisocyanals or substituted hydrocarbon diisocyanals. Lots of such orga frills Polyisocyanates are known in the literature and in practice; may be mentioned

p-phenylene diisocyanate, biphenyl diisocyanate.

Toluene diisocyanate,

3,3'-Dimothyl-4,4'-biphenylcndii_ocyanat,

ίο M-tetramethylenediisocyanai,

I lexamethylndiisoeyanate,
2,2,4-trimethyl-1,6-hydroxylcndiisocyanate,
Methyl bis (phenyl isocyanal).
Lysine methyl ester diisocyanate,

Bis (isocyanate ethyl) fumarate. Isophorone diisocyanate

and methylcycloxyl diisocyanate.
Addition products of diols with terminal isocyanate groups, such as ethylene glycol, can also be used. 1,4-bulylene glycol, polyalkylene glycols

i.a. These compounds are prepared by using more than one mole of a diisocyanate, for example one of the mentioned type, mn converts one mole of a diol to a long-chain diisocyanate. It is also possible add the diol together with the diisocyanate.

While diisocyanates are also preferred, higher polyisocyanates can also be used as part of the organic polyisocyanates can be used, for example 1,2,4-benzene triisocyanate and polymethylene polyphenyl isocyanate.

Preference is given to using aliphatic diisocyanates since, as has been found, these are used in the finished product Coating can achieve better color retention. Examples of such diisocyanates are bis (isocyanatocyclohexyl) methane, 1,4-butylene diisocyanate and methylcyclohexyl diisocyanate. The ratio of the diisocyanate to the polyvalent hydroxyl-containing compound, d. H. to the polyester polyol or polyether polyol is chosen so that one has a hydroxyl group Product received. This can be achieved by the polyisocyanate in a lower than the stoichiometric amount used, d. H. less than one isocyanate group for one hydrocyl and carboxyl group in the polyvalent hydroxyl-containing compound. A higher, i.e. H. a stoichiometric cr or an isocyanate level above this can then be used if the reaction takes place in the desired stage is completed, as is done by adding a compound to the remaining Isocyanate groups reacts. Examples of such compounds are water, alcohols and amines.

To the reaction between the hydroxyl-containing material and the polyisocyanate in a desired One can end a polyfunctional stage of its sequence, which is determined by the viscosity

Add 5 ^r > alcohol, thereby also introducing remaining hydroxyl groups. Amino alcohols such as ethanolamine or diethanolamine are particularly suitable for this purpose, since the amino groups react preferentially with the isocyanate groups present.

wi Also polyols such as ethylene glycol, trimethylolpropane and hydroxyl-terminated polyesters or polyethers can be used for this purpose.

Albeit, generally speaking, the ratio of the components of the polycster polyol. of the polyisocyanate

(.5 and the abortion tool, if used can be varied, every skilled person knows that the amounts must be chosen so that gelling prevented and a non-conforming hydroxyl group halli-

gcs urethane reaction product is obtained. The hydroxyl number of the Urelhan reaction product should at least 10, preferably 20 to about 200.

The urethane reaction product is mixed with an aminoplast (amine-aldehyde resin) to produce the coating material. Aminoplasts are aldehyde condensation products of melamine, urea and similar compounds. Products which are obtained by the reaction of formaldehyde with melamine, urea or benzguanamine are commonly used and preferred for the purposes of the present invention. However, one can also use the condensation products of other amines and amides, e.g. B. Aldchydkondcnsate von Triazinen. Diazines, triazoles, guanidines, guanamines and alkyl- and aryl-substituted derivatives of these compounds, such as alkyl- and aryl-substituted ureas and alkyl- and aryl-substituted melamines. Examples of the latter compounds are
NN-dimethylurea, benzourea,
Dicyandiamide, formylguanamine, acetoguanamine, ammeline, 2-chloro-4,6-diamino-1,3,5-triazine,
6-Melhy 1-2,4-diamino-1,3,4-triazine,
SS-Diaminotriazoi.Triaminopyrimidin,
2-mcrcapto-4,6-diaminopyrimidine,
2,4,6-triethyltriamino-1,3,5-triazine and the like.
Even if formaldehyde is used as the aldehyde in most cases, similar condensation products can also be produced from other aldehydes, for example acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural and others.

The amine-aldehyde condensation products contain Methylol or similar alkylol groups. In most cases, at least part of this will be Alkylol groups etherified by reaction with an alcohol, being in organic solvents soluble resins will be included. Any monohydric alcohol can be used for this purpose, for example methanol, ethanol, propanol, butanol, Pcntanol, Hcxanol. Hcptanol and others, as well as benzyl alcohol and other aromatic alcohols, cyclic alcohols such as cyclohexanol, monoethers of glycol such as diethyl glycol monoethyl ether, and halogen-substituted alcohols or other substituted alcohols such as 3-chloro-propanol. The preferred amine-aldehyde resins are etherified with methanol or butanol. In some cases the alkylol groups of the condensation product to form acyl groups, e.g. B. with acetic acid, implemented, or implemented with amines, for example morpholine.

In order to achieve optimal properties, the coating composition preferably contains a polyester polyol with a low (jlaseinfricrtempcralur, especially a Glaseinfricrtcmperauir below about 25 ° C. The addition such a polymerizing polyol produces a balanced effect Relationship between flexibility and hardness. Optionally in a mixture with a polyester polyol Polyether polyols used have in many cases a low glass temperature. Polyester polyols, which have a low glass temperature, consist in particular of acyclic reactants, such as adipic acid, azelaic acid and alkylcnglycols. l> oly (neopcnlyladi | ial) is a suitable example of this. Other polymeric polyols with good properties are the condensates of l.akloncn with polyols, for example the condensation prodiiki from Caprolaklon and Ethylene glycol, propylene glycol or Tri met hy Io I propane. The amounts used of the components of the coating compositions depend largely on the type of individual components, for example from the aminoplast resin used in each case and from the Type of polyester polyol used. In most cases, the coating composition contains resinous ones Ingredients about 50 to about 95 weight percent urethane reaction product and about 5 to about 50 Weight percent aminoplast resin.

The organic material having a plurality of hydroxyl groups can contain polyether polyols in addition to the polyester polyol included in various ways. Either the polyether polyol can be used in the polyester as part of the Polyol components are present, or an adduct can be made from the polyether polyol and the polyisocyanate or prepare prepolymer with terminal isocyanate groups. A third possibility is that the polymeric polyol as such before or after the reaction of the polyester with the Polyisocyanate mixes with the polyester. The choice of procedure depends on the particular one used Components and the desired properties. In each of these cases, however, contains the received Product both “hard” and “soft” segments in the manner of block copolymers.

The coating compositions according to the invention which are storage-stable in a packaging and therefore also can be referred to as one-pack coating compositions, can be prepared by conventional methods, e.g. B. by Brushing, dipping, flowing, and others. In most cases, however, one wears them by spraying on. The methods and devices customary for this purpose are used for this purpose. They can be used on practically any carrier, such as wood, metal, glass, fabric, plastics, foams

and the like, as well as on primers of various types.

The coatings are cured at elevated temperatures. The hardening happens mostly in the area of about 20 to about 40 minutes at a temperature of 60 ° C. to 127 ° C., but higher or lower temperatures can also be used Temperatures and, in a corresponding manner, shorter and longer times can be used. In detail The curing conditions used also depend on the type of carrier and on the respective for the components used in the preparation. Optionally, acidic catalysts and others can be used Curing catalysts are added as curing aids. Such additives allow use lower temperatures and / or shorter curing times.

The invention is described in more detail by means of the following examples. These examples are intended to enhance the invention explain, but not limit to the details disclosed therein. All in the examples and the in the entire description, parts and percentages are, unless otherwise stated, Parts by weight and percentages by weight.

example 1

bo One fills 126.9 parts of neopantyl glycol, 22.1 parts Trimethylolpropane, 72.3 parts of adipic acid and 123.2 parts of isophthalic acid in a reaction vessel and heat the mixture for 30 minutes to 200 "C and then to 220" C until the resin has the Gardner-HoldtVisko-

h5 sitiit F (60% solids in methyl ethyl ketone), a Acid number of about 10 and a hydroxyl number of about 100 has. 70 parts of the polyester polyol obtained are mixed with 35 parts of methyl ethyl ketone and

7.13 parts of methane bis (cyclohexyl isocyanate), heated the mixture at 65.6 ° C for 20 hours, then cooled to 48.9 ° C for 3 hours and then settled 22 parts n-butanol and 0.3 g ethunolamine too. The product has the Gardner-Holdt viscosity Zl - Z2, a content of about 60% non-volatile solids and the acid number 3.7.

A gray coating composition is produced by the urethane reaction product obtained in a Amount of 196.5 parts with 18.7 parts of hexakis (methoxymethyl) melamine, 15.8 parts of poly (oxetetramethylene glycol, 7.5 parts of a 20% solution of Cellulose acetobutyrate in a mixture of 80 parts of toluene and 20 parts of ethanol, 67.5 parts of a Pigment paste, 217.5 parts of toluene, 49.5 parts of ethylene glycol monoethyl ether acetate, 99 parts of ethylene glycol monoethyl ether, 74.5 parts of diacetone alcohol and 1.5 Mix parts of p-toluenesulfonic acid.

The pigment paste used in this mixture was ground in a solution of a polyester prepared from 146 parts of neopentyl glycol, 112 parts of adipic acid, 191 parts of isophthalic acid and 103 parts of triniethylolpropane. The paste was made by mixing 89 parts of polyester (60% solids in xylene), 260 parts of TiCh, 13 parts of a black pigment, 28 parts of xylene, 43.5 parts of methyl isobutyl ketone, and 10.4 parts of butanol, grinding the mixture in a ball mill until a particle size of 6 ^1/2 Hegman reached, and adding the mixture with 50 parts of toluene.

The coating composition obtained has good storability and excellent properties. For example, when cured at 121 ° C for 60 minutes, a film is obtained which has superior elongation (maximum elongation 181%) and excellent tensile strength (2.09 x 10 ⁵ g / cm as measured in the Instron tester). As a coating on polyurethane foam of the type used for shock absorbers on automobiles (density 0.64 g / ccm with a Shore "A" hardness of 78) it shows satisfactory properties, above all an impact strength of more than 184 cm / kg (measured in a Gardner Variable Impact Tester). The preparation is suitable as a primer for foams of the type mentioned and similar substances.

Example 2

It is made from the urethane reaction product according to Example 1 and one also according to Example 1, but pigment paste prepared without black pigment produces a white coating mass. The pigment contains 61.5% TiO2, 12% polyester and suitable solvents. the The coating compound has the following components:

74 parts of urethane reaction product, 10 parts of hexakis (methoxymethyl) melamine, 40 parts of pigment paste, 6 parts of poly (oxytetramethylene glycol) (mol. Wt. 1000), 5 parts of a cellulose acetobutyrate solution Example 1, 0.5 part of p-toluenesulfonic acid, 100 parts Methyl ethyl ketone and 50 parts of ethylene glycol monoethyl ether acetate.

Films produced from this mass have a maximum elongation of 177% and a tensile strength of 1.55 · 10 ⁵ g / cm ^{2 after a hardening treatment of 60 minutes at 12 ° C..} If the composition is applied as a coating to a primed foam of the type described in Example I, a coated product is obtained which has excellent properties, above all good impact strength.

Example 3

A coating composition is produced according to Example 1,

but uses a commercially available resinous, less highly methylated one instead of the aminoplast resin Melamine formaldehyde resin. The product has similar properties to that of Example 1.

Example 4

According to Example 1, the urethane reaction product described there and that also there are prepared pigment paste described using one of 5.5 moles of formaldehyde and 6 moles of butanol per mole Melamine obtained butylated melamine formaldehyde resin of a coating compound. The resin is applied in the form of a 60% strength solution, whereby Butanol and xylene in a ratio of 25:75 can be used as solvents. The coating compound contains 110 Parts urethane reaction product, 42 parts butylated meiamine resin, 10.5 parts poly (oxytetramethylene) glycol (Mol.wt. 1000), 45 parts of pigment paste, 5 parts of cellulose acetobutyrate solution according to Example 1, 130 parts Xylene, 40 parts of ethylene glycol morioethyl ether acetate, 80 parts of ethylene glycol monoethyl ether, 50 parts of diacetone alcohol and 2 parts of p-toluenesulfonic acid.

With this preparation, stretchable films are obtained which have a somewhat lower maximum elongation than the above-mentioned films, but a good tensile strength (2.65 · 10 ⁵ g / cm- '). When applied to foam like

As described in Example I, the coating has good impact resistance and other properties.

Example 5

A polyester is made, the poly (oxytetramethy-

JS len) glycol in the polyester molecule, from 4875 parts Neopentyl glycol, 3014 parts of adipic acid, 5132 parts of isophthalic acid, 921 parts of trimethylolpropane and 3750 parts Share poly (oxytetramethylene) glycol (mol. Wt. 1000). The polyester obtained has an acid number of 5.9 and the hydroxyl number 59. 1800 parts of this polyester are used in 1080 parts of methyl isobutyl ketone with 168 Share methane bis (cyclohexyl isocyanate) around. One warms up the mixture for 6 1/2 hours at 65.6 ° C and sets 2605 parts of the product obtained 3.9 parts Ethanolamine and 520 parts of Bulanol. The product has a Gardner-Holdt viscosity of Z 3. It contains 51.2% non-volatile solids.

A coating composition is produced from the urethane reaction product obtained by adding it in an amount of 76 parts to 7.5 parts of hexakis (melhoxymethyl) melamine, 37 parts of the pigment paste according to Example 2, 5 parts of cellulose acetobutyrate solution according to Example 1, 60 Parts of Äthylcnglykolmonoäthylätheracctat, 30 parts of methyl ethyl ketone, 80 parts of toluene and 0.75 parts of p-Toluolsulfonsiitire mixes. Films made from this composition, when cured for 30 minutes at I21 "C, have excellent elongation (187% maximum elongation) and an excellent tensile strength wedge (1.86 · 10 ⁵ g / cm ² ) in example 2,

Used as a protective coating, they result in coatings with good overall properties.

Example 6

A mixture is placed in a coupling vessel 1000 parts of poly (oxytetramelhylene) glyc (il (mol. Wt.

1000), 574 parts of polycster polyol (obtained from neopenlyl glycol and adipic acid; Acid number 0.3, hydroxyl number

35), 82.3 parts of 1,4-butanediol, 128.7 parts of lb-1 lcxi'inuiol

ii

and 892.5 parts of dimethylformiamide and are 1220 parts of this mixture with 472 parts of methane bis (cyclohexyl isocyanate, 325 parts of cyclohexanone, 860 parts of dimethylformamide, 8.1 parts of diethylenetriamine and 14.4 parts Divide a 1% solution of dibutyltin acetate in cyclohexanone together. You heat it up like that obtained mixture for 2 '/> hours at 121 "C and gives then 272 parts of butanol and 10.7 parts of diethanolamine are added to 2717 parts of the resin obtained. That Product contains 40.5% non-volatile solids. It has an acid number of 0, fa3.

A coating composition is prepared from the urethane reaction product by mixing it in an amount of 632 parts with 227 parts of pigment paste, 134 parts of methylated melamine-formaldehyde resin, 8 parts of silica pigment, 1110 parts of methyl ethyl ketone, 123 parts of toluene and 4 parts of p-toluenesulfonic acid. The pigment paste used was ground in a solution of 146 parts of neopyl glycol, 112 parts of adipic acid, 191 parts of isophthalic acid and 103 parts of trimethylolpropane. The paste is made by mixing 89 parts of polyester (60% solids in xylene), 260 parts of TiO ₂ , 28 parts of xylene, 43.5 parts of methyl isobutyl ketone, and 10.5 parts of butanol. This mixture is ground in a ball mill until a particle size of 6V2 Hegman is reached, whereupon 50 parts of toluene are added.

The coating composition obtained has good storability and excellent properties. If you apply it to poly (vinyl chloride) foam and cure for 30 minutes at 121 ° C, you get a coating with good impact strength at low temperatures and good tensile strength (2.5 x ^{10 5} g / cm ² , measured with the Instron Testing device).

Example 7

The procedure is as in Example 6, but hexakis (methoxymethyl) melamine is used as the aminoplast resin. The properties are essentially the same as in Example 6.

Example 8

The procedure is as in Example 6, but one with 5.5 moles of formaldehyde and 6 moles of butanol to 1 mole is used Melamine produced butylated melamine formaldehyde resin as an aminoplast resin. Good results are obtained.

Example 9

The procedure is as in Example 6, but a 352 parts poly (oxytetramethylene) glycol (MoL-wt. 1000), 34 parts of 1,4-butanediol, 45 parts of 1,6-hexanediol, 202 parts of polyester polyol according to the example I and 367 parts of methane bistcyclohexyl isocyanate) urethane reaction product. The results are essentially the same as the results obtained in Example 6.

Claims (6)

Patent claims: 1. Storage-stable coating mass in one Packaging off a) a reaction product containing urethane ribs a polyisocyanate and a polyfunctional compound, b) an aminoplast, c) an organic solvent and optionally d) usual additives, characterized in that it is a ungelled hydroxyl-containing urethane reaction product of an organic polyisocyanal and of an organic material with multiple hydroxyl groups, with a greater proportion of this Material is a polyester polyol made from (a) an alcohol component having an average functionality of at least about 1.9 and (b) an acid component has been prepared consisting essentially of one or more Carboxylic acids or their anhydrides with 2 to 14 carbon atoms in the molecule and has an average functionality of at least 1.9, wherein the alcohol component and the acid component a total of no more than about 1 gram-mole of compounds with a functionality of 3 or more per 500 g of the alcohol component plus acid component included. 2. coating composition according to claim I, characterized in that the material with several Hydroxyl groups of the urethane reaction product in addition to; Polyester polyol Polyether polyol having a hydroxyl equivalent of at least about 100 and a total of no more than about one gram-mole of compounds having a functionality of 3 or more Contains 500 g of the polyether polyol. 3. coating composition according to claim 1 or 2, characterized in that the material with several hydroxyl groups of the urethane reaction product in addition to the polyester polyol still contains a low molecular weight diol. 4. Coating composition according to one of claims 1 to 3, characterized in that the urethane reaction product has a hydroxyl number of at least 10 Has. 5. Coating composition according to one of claims I to 4, characterized in that the Urethanumsetzungsprodukt contains a polyester polyol having a Glaseinfriertemperatur below about 25 ⁰ C. 6. Use of the coating composition according to any one of claims i to 5 for coating rubbery elastic substrates.