DE2025173A1 - Coating compound - Google Patents

Description

Dr. Michael May

Patent attorney 635 Bad Nauhaim

Barrjr. "E. Ut)

Telephone, Ci ...: ^ > _2 λ 7

(190)

PPG Industries, Inc., Pittsburgh, PA, USA

coating compound

This invention relates to a coating composition suitable for making stretchable coatings and to a urethane reaction product containing hydroxyl groups a polyester component or a polyether component and an amine-aldehyde resin.

More recent developments in the technology of manufacturing occur. Coatings have resulted in coatings that are suitable for application to difficult-to-coat substrates of various types and have a number of different properties. Coatings with an excellent appearance are obtained excellent durability under harsh environmental conditions are persistent. The coatings for which higher demands are made include those of vehicles, for example of automobiles that are also under the influence weather and various other forms of wear and tear.

Recently, interest has turned to the use of rubber-like elastic fabrics for articles that exposed to mechanical shock or shock loads are protruding like shock absorbers and molded parts of automobiles Corners and surfaces of machines in industry, Floor strips and other parts of doors and house entrances

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and the like. The use of these substances gives increased protection against permanent damage in the material structure, but you need to To give objects a desired appearance, their surface provided with a decorative protective coating, which can also be damaged during use. The coatings of the common types, including those previously used on rubber and similar stretchable objects, however, do not have the required combination of properties. These properties are:

1. Extensibility: This property is necessary in order to take advantage of the elastic or resilient backing can reach their full effect without damaging the uniform surface of the coating.

2. Tensile strength «A high level of tensile strength is necessary to prevent the film from cracking in use.

3. Package stability: For the purpose of easy handling in use, the liquid coating mixture must be given below Conditions can be stable for a long time without the resin contained therein being allowed to 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 is exposed to sunlight, weather and similar influences.

5. Impact resistance: The coating must have impact resistance have at different temperatures, which correspond to temperatures as they occur in extreme weather conditions, d. H. Temperatures between -29 ° C and + 49 ° C.

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6. Adhesion: The coating must have the ability to sufficiently to adhere strongly to the various substrates to which it is applied, e.g. B. stretchy fabrics, such as Soles, qumad, and the like, and metals such as mild steel. In addition, the coatings must have an intermediate layer have sufficient adhesive strength to other coating layers and to various types of primer / primer.

7. Resistance to chemicals and moisture: These Properties relate to the durability of the coatings against saponification under the action of acids and alkalis, their resistance to various solvents and their resistance to an atmosphere of high humidity and great warmth.

8. Resistance to cracking in the temperature-humidity cycle This property is important when the top cover is exposed to rapid changes in temperature and humidity, such as that of automobiles on the move or may be subject to during storage. This property is tested by using the Coating coated object alternately exposed to high temperatures and high humidity and low Exposed to temperatures and low humidity.

Other properties which are important for the usability of the coating smells 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 get the above properties in to achieve their entirety, as one or more of the desired properties in most cases the use

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Clay substances and preparations require that usually cause a deterioration in the other properties desired.

They registers or preparations according to the present invention consist of (1) a non-gelled, hydroxyl group containing urethane decomposition product of an organic Polyisoeyanat and a polyvalent compound, in particular an organic compound with several hydroxyl groups, which contains as its main ingredient a substantially linear polyester or a polyether glycol, and (2) one Aainaldehydhars.

The polyester is made from an alcohol component with an average functionality of at least about 1.9 and an acid component consisting essentially of one or more monomeric carboxylic acids or anhydrides with 2 to 14 carbon atoms and also has an average functionality of at least about 1.9. The alcohols used may be used so that the desired elasticity and other properties are obtained and acids or anhydrides contain no more than a total of about one gram-mole of compounds having a functionality of 3 or more per 500 grams of the total amount of used Have alcohols and acid or anhydride.

The polyether polyol has a hydrozyl equivalent of at least about 10O _1, usually from about 100 to about 10,000. (By "hydrosyl equivalent" is meant the weight per hydroxyl group.) In order to obtain the desired elongation and other properties, the polyether polyol must not exceed about a total of one gram-mole of compounds with a functionality of 3 or more per 500 g of the total of the components from which it is made.

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plating · this type can be fixed on practically any Supports are applied · Particularly suitable rubbery, elastic substrates or supports such as polyurethane and polyethylene soles, natural and synthetic rubber, rubber foam, and various elastomers Plastics. They can also be used with particular advantage on other substrates such as mild steel and aluminum.

These preparations, although produced on the basis of urethane, differ from conventional polyurethanes in that they are stable in storage in a package and still result in a cross-linked, heat-cured coating.

The coatings of the invention have those mentioned above Properties to a satisfactory degree and in a combination that has not been achievable by known methods.

The preparations according to the invention contain, as one of the components, an isocyanate-modified, hydroxyl-containing Hars, which is obtained by a essentially linear polyester polyol or a polyether polyol containing polyvalent compound with a polyiso, -oyanate. For the production of the coating composition according to Irfindung the isocyanate-modified resin with a lminoplasthars mixed.

The polyester polyol or polyether polyol used must have certain properties so that a coating with the desired characteristics is obtained. These properties are generally obtained by either one a polyol having an average functionality of at least about 1.9 containing polyester or a poly (hexylene) polyol (or a mixture of polyols) which relatively long chains per hydro ^ oil group and therefore one

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Hydroxyllottiralent tob at least about 100, preferably τοπ at least about 300 has. Sit consists of a polyol component in "most cases essentially" one or a lot Diols. If the polyether polyol component is not more than Containing about 1 grass mole of compounds which contain three or more hydroxyl groups per 300 g of the weighted weight, one can also use triols or higher polyols alone or use sub part. Even though it is not always necessary to work with a triol or higher poly oil, then do so a certain branching is after all two-kBed; however should the polyether or polyester should not be highly branched. You can also add a small amount of a monoalcohol, especially if larger amounts of higher amounts Polyols are used. If, in certain cases, very high molecular weight polyols are used, these can largely or entirely consist of compounds with a Functionality of more than 2 exist.

Diols of the kind commonly used in 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, Oyelohoxane disethanol, caprolactone diol (the reaction product from oaprolactone and ethylene glycol), hydroxyalkyl ortβ bisphenols, polyether glycols, for example poly (ozytetramethylene) glycol and the like of different types and, as said, polyols with a higher functionality can also be used. as Polyols of this type are, for example, trimethylolpropane, Trisethylolethane, pentaerythritol and the like, and furthermore polyols of higher molecular weight, such as those produced by the transalkylation of lower molecular weight polyols are obtained, called. An example of such a higher molecular weight polyol is the reaction product of 20 get ethylene azide and 1 mole trisethylolpropane.

The acid component of the polyester consists essentially of monomeric carboxylic acids or anhydrides with 2 to 14 Carbon atoms per molecule. The acids should have a pass-through functionality of at least about 1.9. In most cases, the acid component contains at least about 75 mol% of dicarboxylic acids or their anhydrides. The functionality of the acid component is based on similar considerations in connection with the alcohol component were determinative, with the overall functionality of the system is under consideration.

Examples of acids that can be used are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, Hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, malic acid, glutaric acid, chiorenedioic acid, tetrachlorophthalic acid and other dicarboxylic acids of various kinds Art. The polyesters may contain minor amounts of a monobasic acid such as benzoic acid. You can also get higher Polycarboxylic acids, such as trieallitic acid and tricarballyic acid, use. Where acids are known above, the anhydrides of these acids can of course also be used, insofar as these Forming anhydrides are used instead of acids. The polyester preferably contains, at least as part of, the Acid component, an aliphatic dicarboxylic acid.

Preferred polyether polyols are poly (oxyalkylene) glycols of the formula.

.0 (CH)

ι ^η

OH

in which B is hydrogen or a lower alkyl radical, η for a number from 2 to 6 and m for a number from 2 to 100 or more. Examples are poly (ozytetramethylene) glycols, poly (oayethylene) glycols, poly (ozytrimethylene) ^

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glycols, poly (oxypentaMethylene) glycols, polypropylene glycols i.a. Prevented polyethylene glycols are of this class Poly (oxyrtttr * methylen) glycol · with a «molecular weight Clay about 400 to about 10,000.

Hay can also use pelyether polyols which are produced by the oxyalkylation of polyeles of various kinds, for example wide-ranging glycols such as ethylene glycol, 1,6-hexanediol and the like, or higher polyols such as trimethylolpropane, trimethylol-itheu, pentaerythritol and the like. polyols of higher Funktionalitlt _t. which can be used as stated can be prepared by oxyalkylating compounds such as sorbitol or sucrose. One of the common oxalkylation methods is that a polyol with an alkylene oxide, e.g. B. ethylene or propylene azide, in the presence of an acidic or basic catalyst.

unions of poly & therpolyols or of polyols, the residues ▼ on different structure can also contain be used.

As stated, the overall functionality per unit weight of the polyether polyol is important. The polyether polyol should no more than about one gram-mole of compounds having a punctiformity of 3 or more per 500 grams of total weight of the poly & therpolyol, i.e. it should no longer be made of al · be prepared from the stated amount of compounds. "Functionality" means the number of reactive ones Hydroxyl groups (and any carboxyl groups present) per molecule. Certain compounds contain both Hydroxyl * as well as carboxyl groups, for example 6-hydroxyhexanecarboxylic acid, e-hydroxyoctanecarboxylic acid, tartaric acid and others.

If a polyester polyol is used, no more should be used ale about 1 gram-mole of acids and / or alcohols with the functionality 3 or more to 500 g of the total weight of these

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Connections are worked · Under "functionality" is understood here the number of reactive hydroxyl and Carboxyl groups per molecule, with anhydride groups being two carboxyl groups equivalent.

In addition to the processes mentioned, the polyether polyol can also be produced using any of the known processes, the reaction conditions and the ratio of the reactants being chosen so that a product with residual hydroxyl groups is obtained, namely a polyether polyol with a hydroxyl equivalent of at least about 100, but preferably not more than about 10,000

The polyester is prepared by known processes, the reaction conditions and the ratio of the reactants being chosen so that a product with remaining Hydroxyl groups are formed. The number of hydroxyl groups contained in the product can vary, but the hydroxyl number should be at least about 30, preferably more than 80.

Old polyvalent material within the meaning of the present invention can also be mixtures of polyester polyols and polyether polyols together with smaller amounts of other hydroxyl-containing compounds, such as monomeric polyols, especially biols, such as 1,4-butanediol, keopentyl glycol and the like, monohydric alcohols and polyfunctional compounds having one or more hydroxyl groups such as ethanolamine can be used. Are suitable also compounds that have other active, hydrogen-containing groups contain, such as water and polyfunctional amines. Examples are! Isophoronediamine, p-menthediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethanolamine and others.

As an organic polyisooyanate, as described, with the multi-valued connection is implemented, one can in principle » borrowed any Polyisooyanat use, for example Eohlen-

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hydrogen polyisocyanates or substituted hydrocarbon diisocyanates. Much love organic polyisocyanates are known in literature and practice; p-Phenylenediisoeyanate, Biphenyldiieooyanat, Toluylenedilsooyanat, 3,3'- Dimethyl- ^ V-biphenylene diisooyanate, 1,4-tetramethylene diisooyanate, hexamethylene diisocyanate, 2,2,4-irimethyl-1,6-hexylene diisocyanate, methylene-bis-phenyl isocyanate), lye methyl ester diiaovyanate, bis- (iaocyanato ethyl) fumarloisocyanate and methyl isocyanato diisocyanate diisocyanate diisocyanate diisocyanate diisocyanate. One can Also, addition products of diols with terminal isocyanate groups, such as ethylene glycol, 1,4-butylene glycol, polyalkylene glycols and others. These compounds are made using more than a mole of a diisocyanate, for example one of the type mentioned, reacts with one mole of a diol su a long-chain diocyanate. It is also possible to add the diol together with the diocyanate.

If diisocyanates are also preferably used, so can higher polyisocyanates can also be used as part of the organic polyisocyanates, for example 1,2,4-benzene tri-isocyanate and polymethylene polyphenyl isocyanate.

It is preferred to use aliphatic diisocyanates, since one with these, as was found, one in the finished upper cover can achieve better color retention. Examples of such Diisocyanates are bis (isocyanatocyclohexyl) methane, 1,4-butylene diisocyanate and methylcyclohexyldilsoeyanate. That Ratio of the diisocyanate to the polyvalent hydroxyl-containing compound, d. H. for the polyester polyol or polyether polyol is chosen so that a hydroxyl group-containing Product received. This can be achieved by using the polyisocyanate in less than the etoichiometric amount; H. less than an isoeyanate group to a hydroxyl and carboxyl group in the polyvalent hydroxyl group-containing compound. A high® ^ d. H. a

• '0OSiSO- / 2OT? .'- ^ -

stoichiometric or an additional isocyanate level can then be used if the reaction in the desired stage is ended, as is done by adding a compound happens that reacts with the remaining isocyanate groups. Examples of such compounds are water, Alcohols and amines.

According to a particularly expedient embodiment of the invention, a polyfunctional alcohol is used in order to terminate the reaction in the desired stage of its course, which is determined by the viscosity, which also introduces remaining hydroxyl groups. Amino alcohols such as ethanolamine, diethanoi φ amln and the like are particularly suitable for this purpose, since the amino groups react preferentially with the Ϊ socjanat groups present. Polyols such as ethylene glycol, trimethylolpropane and polyester or polyethers with terminal hydroxyl groups can also be used for this purpose.

Even if, generally speaking, the ratio of the components of the polyester polyol or polyether polyol, the polyisocyanate and any terminating agent used can be varied, then every person skilled in the art knows that the amounts are chosen so as to prevent gelling and that which contain non-gelled hydroxyl groups Urethane reaction product is obtained. The hydroxyl number of the urethane reaction product must be at least 10, preferably 20 to about 200. φ

The urethane conversion product described is used in manufacture the coating compound old an aminoplast resin (amine-aldehyde resin) mixed. Aminoplast resins 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 generally in use and for the purposes of the present invention preferred. However, one can also use the condensation products use other amines and amides, e.g. B. aldehyde condensates of triazines, diazines, triazoles, guanidines, guanamines

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as well as 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 N.N-dimethylurea, benzourea, Dicyandiamide, formylguanamine, acetoguanamine, ammeline, 2-chloro-4,6-diamino-1,3,5-triazine, 6-methyl-2,4 ~ diamino-1,3,4-triazine, 3,5-diaminotriazole, triaminopyrimidine, 2-mercapto-4,6-diaminopyrimldine, 2,4-, 6-triethyltriamino-i, 3,5-triazine and the like.

If formaldehyde is used as aldehyde in most cases, similar condensation products can also be used from other aldehydes, for example acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfurolu. a. manufactured will.

The amine-aldehyde condensation products contain methylol or similar alkylol groups. In most cases, at least some of these alkylol groups are reacted etherified with an alcohol, resins soluble in organic solvents being obtained. For this purpose you can use any monohydric alcohol, for example Methanol, ethanol, propanol, butanol, pentanol, hexanol, Heptanol and others, as well as benzyl alcohol and other aromatic alcohols, cyclic alcohols such as cyclohexanol, monoethers of the glycols, such as diethylene glycol monoethyl ether, and halogen-substituted or other substituted alcohols, such as 3-chloropropanol. The preferred amine-aldehyde resins are with Etherified methanol or butanol. In some cases the alkylol groups of the condensation product are formed from acyl groups, e.g. B. reacted with acetic acid, or with Amines, for example morpholine, implemented.

In order to achieve optimal properties, the preparation preferably contains a polymeric polyol, i. H. a polyester polyol or polyether polyol, having a low glass transition temperature, d. H. a glass freezing temperature below

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about 23 ° G. The addition of such a polymeric polyol creates a balance between flexibility and hardness. In many cases the polyether polyol used has been the desired glass freezing temperature. If you want to add a component of this kind, you can add it to the abovementioned polyether polyols or in their place one of the many polyester polyols which has the desired glass transition temperature, especially those from acyclic reactants such as adipic acid, azelaic acid and alkylene glycols are produced. Poly (neopentyl adipate) is a suitable example of this. Other polymeric polyols with good properties are the condensates of lactones Polyols, for example the condensation product of caprolactone and ethylene glycol, propylene glycol, trimethylolpropane and the like

If the polyether polyol used has a low glass freezing temperature, it is often found that the coating does not have the appropriate hardness. It is therefore useful in many cases, the "soft" polyether polyol together with a to use a smaller amount of a polyester polyol or its components which have a higher glass transition temperature. For this purpose you can either use polyester residues in bring in the polyether molecule or from the polyester polyol and the polyisocyanate to produce an addition product or prepolymer with terminal isocyanate groups. A third The procedure is that the polyester polyol as such before or after the reaction of the polyester with the Polyisocyanate bit mixed with the polyether polyol. One can also with the addition of low molecular weight diols or diamines work. The choice of procedure depends on the particular components used and the desired properties. In any event, however, the product obtained contains both “hard” and “soft” segments of the blook copolymers type.

The proportions of the components mentioned can be used for

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Creation of certain properties can be varied. For example, a higher polyether polyol content gives something softer and more pliable overlie, while one harder and more resistant oversize is obtained if the amount of aminoplaatha is increased. The quantities used depend largely on the type of one of its components, for example from of the polyether glycol used, and aminoplast resin and, if appropriate, of the type of polyester polyol used. In most cases, the total preparation contains about 50 to about 95 weight percent urethane reaction product and about 5 to about 50 weight percent aminoplast resin.

™ The polymeric polyol can be incorporated into the preparation in various ways. In some cases, the polyester polyol used can serve as any polymeric polyol, however as a rule, no coating of satisfactory hardness is obtained. It is more expedient to use a "soft" polymeric polyol together with a polyester polyol (or its Ingredients), which has a higher glass transition temperature. The procedure here is that either the polymeric polyol introducing into the polyester as part of the polyol component or that one of the polymer polyol and the polyisocyanate Addition product or prepolymer with terminal isocyanate groups. A third approach exists

α is that the polymeric polyol as such is mixed with the polyester before or after the reaction of the polyester with the polyisocyanate. The choice of procedure depends on the particular components used and the properties desired. In any case, however, the product obtained contains both "hard" and "soft" segments of the Bloek copolymer type.

The masses or preparations according to the invention, which are storage-stable in a packaging and can therefore also be referred to as Einpaok coating masses, can be prepared by conventional methods, e.g. by spreading on, dipping,

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Flow, inter alia, can be applied. In most In cases, however, they are deceived by spraying them on. The procedures customary for this purpose are used for this purpose and fixtures. You can use practically any carrier, such as wood, metal, glass, fabric, plastics, foams and the like, as well as various types of primer.

The coatings are cured at elevated temperatures. The curing is done mostly in the range of about 20 to about 60 minutes at a temperature of ° C to 127 ° C, 1edoch _t can also higher or lower temperatures and shorter and longer times in a corresponding manner be used. In detail, the curing conditions used also depend on the type of carrier and on the components used in each case for the preparation. If necessary, acidic catalysts and other curing catalysts can be added as curing aids. Such additives allow the use of 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 explain the invention however, it is not limited to the details disclosed therein. All parts and percentages cited in the examples and throughout the description are unless otherwise is said to be parts by weight and percentages by weight.

example 1

126.9 parts of neopentyl glycol, 22.1 parts of trimethylolpropane, 72.3 parts of adipic acid and 123.2 parts of isophthalic acid are poured into a reaction vessel and the mixture is heated at 200 ° C. for 30 minutes and then to 220 ° C. until the resin is obtained the Gardner-Holdt viscosity F (6O % solids in methyl ethyl ketone), a

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Has an acid number of about 10 and a hydroxyl number of about 100. Nan eiecht the obtained Polyeeterpolyol with 70 parts of poly. ester, 35 parts of methyl ethyl ketone and 7.13 parts of methane bis (cyclohexyl isocyanate) (Mobay D-244), the mixture is heated to 65 ° 6 ° O _{1 for} 20 hours and then cooled to 48.9 ° C. for 3 hours and then adds? 2 parts of n-butanol and 0 _{t of} 3 g of ethenolamine. The product has a Gardner-H.oldt viscosity Z1-Z2 ", a content of about 60% non-volatile solids and an acid number of 3.7.

A gray coating mass is produced by illuminating the ' tene tetraethane reaction product in an amount of 196.5 parts with 18.7 parts of hexakis (metho3symethyl) melamine ("CVmel 301"), 15.8 parts of poly (oxytetramethylene) glycol, 7.5 parts of GAB solution (20% solution of "1/2 second oil acetate butyrate" 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 cellosolve acetate, 99 parts of ethyl cellosove, 74.5 Parts of diacetone alcohol and 1.5 parts. p-toluene sulfonic acid mixes.

The pigment paste used in this mixture was ground in a solution of an ester prepared from 146 parts of neopentyl glycol, 112 parts of adipic acid, 191 parts of isophthalic acid and 103 parts of trimethylolpropane. The paste was made by mixing 89 parts of polyester (60% solids in xylene), 260 parts of TiO ₂ , 13 parts of Molacco Black, 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 is reached, and adding 50 parts of toluene to the mixture.

The coating composition obtained has a good shelf life and excellent properties. For example, if you deny them

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Cured at 121 ° C. for 60 minutes, a film is obtained of outstanding elongation (maximum elongation 181%) and excellent tensile strength (2.09 χ 1Cr g / cm measured in Instron test apparatus). As a cover on polyurethane foam from the Kind of how it is used for shock absorbers on automobiles (density (40 lbs / cu.ft - 0.64 g / ccm) with a Shore "A" hardness of 78) it exhibits satisfactory properties, especially an impact strength greater than 60 inches / lbs (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

A white coating mass is produced from the Ilrethane reaction product according to Example 1 and a pigment paste also prepared according to Example 1, but without Molacco Black. The pigment contains 61.5 % TiO ₂ , 12 % polyester and suitable solvents. The coating compound has the following ingredients

74 parts of urethane reaction product, 10 parts of hexakis (methoxymethyl) melamine ("Oymel 301"), 40 parts of pigment paste, 6 parts Poly (oxytetramethylene glycol (mol. Wt. 1000), 5 parts of a GAB solution according to Example 1, 0.5 part of p-toluenesulfonic acid, 100 parts of methyl ethyl ketone and 50 parts of olelosolve acetate.

Films produced from this mass have a maximum after a curing treatment of 60 minutes at 121 ° 0 Elongation of 177% and a tensile strength of 1.55 x 10 ^ g / cm. If you have the mass as a coating on you with a If the foam provided with a base coat of the type described in Example 1 is applied, a coated one is obtained Product with excellent properties, especially good impact strength.

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Example 3

A general description is made similar to Example 1, but instead of the aainoplast resin, the more resinous, less highly ethylated melamine- formaldehyde resin known as "QH-483" is used. The product has similar properties to the one in the example

Example 4

It is prepared according to Example 1 from the urethane reaction product described there and the pigment paste also described there using one of 5-5 moles of formaldehyde and 6 moles. Butanol per mole of melamine butylated melamine-formaldehyde resin obtained a coating composition. The resin is applied in the form of a 60% solids solution, with butanol and xylene in a ratio of 25:75 being used as solvents. The coating composition contains 110 parts of urethane reaction product, 42 parts of butylated melamine resin, 10.5 parts of poly (oxytetramethylene) glycol (mol. Wt. 1000), 45 parts of pigment paste, 5 parts of CAB solution according to Example 1, 130 parts of xylene, 40 parts Cellosolve acetate, 80 parts of ethyl cellosolve, 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 g / cm). When applied to foam as described in Example 1, the coating has good impact resistance and other properties.

Example 5 · -.

A polyester that contains poly (oxytetramethylene) glycol in the polyester molecule is made from 4875 parts of neopentyl glycol, 3014 parts of adipic acid, 5132 parts of isophthalic acid, 921 parts Trimethylol propane and 3750 parts of poly (oxytetramethylene) glycol (Mol. Wt. 1000). The polyester obtained has an acid number of 5.9 and a hydroxyl number of 59. 1800 parts are set

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this polyester in 1080 parts of methyl isobutyl ketone 168 divide Metheii-bie (eyolohexyliiooyanat) "HyIβne V". The mixture is heated to 65.6 ° G and for 6 1/2 hours sets 2605 parts of the product obtained, 3.9 parts of ethanolamine and 520 parts of butanol, see below. The product has a Gardner-Holdt viscosity tone ZJ. It contains 51.2% non-volatile Solids.

Han uses the urethane reaction product obtained to produce a coating composition by adding it to 7.5 parts of hexakie (methoxyaethyl) melamine ("Oymel 301"), 37 parts of the pigment paste according to Example 2, 5 parts the CAB solution naoh Example 1, 60 parts of Cellosolve acetate, 30 parts of methyl ethyl ketone, 80 parts of toluene and 0.75 part of p-ToluoleulfoneSure mixes. Films made from this mass have excellent elasticity when they cure for 30 minutes at 121 ° C. (187% maximum elongation) and excellent tensile strength (1.86 ζ 10 ⁷ g / cm). When used as a protective coating, as in Example 2, they give coatings with good overall properties.

Example 6

A mixture of 1000 parts is placed in a reaction vessel Poly (octetraethylene) glycol (mol. Wt. 1000), 574 parts Polyether polyol (obtained from neopentyl glycol and adipic acid; Slureeehl §, 3, hydroxyl number 35), 82.3 parts 1,4-butanediol, 128.7 parts of 1,6-hexanediol and 892.5 parts of dimethylformamide and gives 1220 parts of this mixture with 472 parts of methane bis (cyolohexylisoejranat ("Hylene W"), 325 parts of cyclohexanone, 860 parts of dimethylformamide, 8.1 parts of diethylenetriamine and 14.4 parts of a 1% solution το η dibutylsinnaoetat in Cyclohexanone together. The mixture thus obtained is heated 2 1/2 hours at 121 ° C and then give in 2717 parts of the resin obtained 272 parts of butanol and 10.7 parts

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Dlftthanolaaln hinxu. Dai product contains 40.5% non-volatile Solid Eb has the acid steel 0.65

nan produces a coating mass from the urethane reaction product, while it is mixed in an amount of 632 parts with 227 parts of pigment paste, 134 parts of methylated melamine ^{formaldehyde hair (H} QR-483 "), 8 parts of silica pigment (" Atq Silioa "), 1110 parts of methyl ethyl ketone The pigment paste used 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 trimethylolpropane (60 % solids in xylene), 260 parts of TiO ₂ , 28 parts of xylene, 4-3.5 parts of methyl isobutyl clay and 10.5 parts of butanol.This mixture is ground in a ball mill to a particle size of 6 1/2 Hegaan is reached, whereupon 50 parts of toluene are added.

The coating composition obtained has good storability and excellent properties. When applied to poly (vinyl chloride) foam, and 30 minutes cured at 121 ° G, to obtain a coating of good impact strength at low temperatures (3 ft.-lbs.ats.-20 ⁰ F) and good tensile strength (2 , 5 xwg / cm, measured with the Instron »tester).

Example 7

The procedure is as in Example 6, but hexakis (methosymethyl) melamine ("Cymel 30Ö ^w )" is used as the aminoplast resin. The properties are essentially the same as in Example 6.

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Beiapi ·! 8th

The procedure is as in Example 6, but a 5.5 is used No formaldehyde and 6 moles of butanol to 1 mole of melamine butylating melamine formaldehyde resin as aminoplast resin. Good results are obtained.

Example 9

Work as in Example 6, but use one from 352 Parts of poly (oxytetramethylene) glycol (Mol.Gew. 1000), 34 parts of 1,4-butanediol, 45 parts of 1,6-hexanediol, 202 parts of polyester polypl according to Example 1 and 36? Parts of methane bis (cyclohexyl isocyanate) produced urethane reaction product. the Results are essentially the same as those obtained in Example 6.

Example 10

To prepare a urethane reaction product which is used in a manner corresponding to the preceding examples, 500 parts of poly (oxyteti ^> amethylene) glycol (mol. Weight 1000), 105 parts of 1,4-butanediol, 150 parts of 1.6 are added Hexanediol, 30 parts of trimethyl! Propane and 1835 parts of methyl isobutyl ketone together and uses 1000 parts of this mixture of 292 parts of methane bis (cyclohexyl isocyanate), 680 parts of methyl isobutyl ketone and 2 parts of a 1% solution of dibutyltin diacetate in methyl isobutyl ketone second mixture * u . The resulting total mixture is heated to 230 ° C. for 10 hours and then 30 parts of Buntanol per 100 parts of resin are added.

Example 11

In a manner similar to Example 10, a urethane reaction product is prepared from 500 parts of poly (oxytetramethylene) glycol 10.5 parts of ieophoronediamine, 3 parts of diethanolamine, 85 parts 1,4-butanediol and 300 parts of tolylene diisocyanate (80%

008850/2017

2,4-1 further, 20 % 2,6-isomer «e). If the product is used in the manner described in the Yorg & ngien examples, coatings with satisfactory properties are obtained.

In the same way, coating compositions with good properties are obtained if instead of those mentioned in the examples Polyethers and polyisocyanates other polyether polyols and other polyester polyols and other polyisocyanates are used. You can also use other polyols than the diols mentioned in the examples, for example monomeric diols and triols, use.

The foregoing description sets forth the invention and embodiments of the invention according to which they are instantly made can best be realized. However, within the scope of the following claims, the invention may also be other than that in FIG specifically described manner.

Claims (1)

Patent not accepted 1. Storage ready-to-use coating compound, consisting of (A) a non-gelled hydroxyl group-containing Urethane reaction product of an organic polyisocyanate and a «material with several hydroxyl groups, which has a larger proportion of one Component contains that (1) 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 consisting essentially of one or more carboxylic acids or anhydrides having 2 to 14 carbon atoms in the molecule and having an average functionality of at least about 1.9, wherein said alcohol component and said acid component contain a total of no more than about one gram-mole of compounds having a functionality of 3 or more per 500 grams of the alcohol component plus acid component, or (2) a polyether polyol having a hydroxy 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 per 500 g of the polyfither polyol and (6) made of an aminoplast resin 008650/2017 2. Coating composition according to claim 1, characterized in that that egg · tin polymeric polyol with a glass freezing temperature contains below about 25 ° C. 3. coating composition according to claim 2, characterized in that the polymeric polyol is reacted with the organic polyisocyanate. 4 ·. Coating compound according to Claim 2, characterized in that the polymeric polyol is mixed with the urethane reaction product and the aminoplast resin. 5. Coating composition according to claim 2, characterized in that that a polyester polyol is used as the polymeric polyol. 6. coating composition according to claim 5 t, characterized in that the polymeric polyol is the conversion product of adipic acid and neopentyl glycol are used. 7. Coating composition according to claim 1, characterized in that the polyester polyol has a hydroxyl number of at least about 30 has. R. coating composition according to claim 1, characterized in that 3ass the urethane reaction product has a hydroxyl number of at least has about 10. 9. Coating composition according to claim 1, characterized in that the isocyanate groups and the reactive ΕγάτοχγΙ- and carboxyl groups are used in a ratio of less than 1s1. 10. coating composition according to claim 1, characterized in that A polyfunctional alcohol is added to the reaction product of organic polyisocyanate and polyester polyol will. 009850/2017 11. A coating composition according to claim 1, characterized in that the aminoplast resin is an alkylated condensation product aue formaldehyde and melamine or urea or Benzoguanamine used. 12. Coating composition according to claim 1, characterized in that a poly (oxyalkylene) glycol is used as the polyether polyol, 13. Coating composition according to claim 12, characterized in that the poly (oxyalkylene) glycol used, poly (oxytetramethylene) glycol is. 14. Process for the preparation of a non-gelled hydroxy-containing Urethane reaction product, characterized in that that he (A) Prepares a polyester polyol from an organic one Polyisocyanate and a material with multiple hydroxyl groups, containing a major proportion of a polyester polyol made from (1) an alcohol component having an average functionality of at least about 1.9 and (2) an acid component consisting essentially of one or more carboxylic acids or anhydrides with 2 to 14 carbon atoms in the molecule and an average functionality of at least has about 1.9, wherein said alcohol component and said acid component a total of not more than about 1 gram-mole of compounds with a functionality of 3 or more per 500 g contain the alcohol component plus acid component, 009650/2017 (B) the Polyeeterpolyol thus prepared with a organic polyisocyanate and (G) terminating the reaction by adding a polyfunctional alcohol to the reaction mixture. 15 · The method according to claim 14, characterized in that an amino alcohol is used as the polyfunctional alcohol. 16. The method according to claim 15, characterized in that the amino alcohol used is ethanolamine or diethanolamine. 17. The method according to claim 14, characterized in that the reaction mixture is a polymeric polyol with a glass transition temperature of less than about 25 ° G. 18. The method according to claim 1 ?, characterized in that a poly (oxyalkylene) glycol is used as the polymeric polyol. ^ 9. Method according to claim 18, characterized in that the used poly (oxyalkylene) glycol poly (oxytetramethylene) glycol is. 20 ". Method according to claim 17, characterized in that the polymeric polyol used is a pelyester polyol. 21. Method according to Aaspmefe "20, claimreli because »used polyester poly ©! las fJmee'fe ^ iaagsprodukt aas Adipic acid and Heopentylglyk®! is"