DE1106015B - Process for the production of thixotropic lacquer binders - Google Patents

Description

Process for the production of thixotropic lacquer binders. Subject This invention is a process for making thixotropic ester binders, how they z. B. as a basis for varnishes, paints, printing inks and adhesives Can be used. As examples of such binders based from esters like natural and synthetic drying oils, through higher fatty acids modified alkyd resins and epoxy resin esters, maleic oils and copolymers unsaturated ester binder of the aforementioned type with vinyl compounds such as styrene, be mentioned, finally also the known combinations of such esters with natural or synthetic resins.

It is already known such binders based of esters thixotropic properties due to the incorporation of polyamides polymeric to give higher fatty acids. The union is made by heating.

It has now been found that thixotropic ester binders with special Advantage can be produced in a technically simple manner that one Ester binders combined with such polyester amides in the heat, their mixture from 3 parts by weight of polyester amide and 7 parts by weight of mineral spirits at room temperature is inhomogeneous and its polar group content does not exceed 35 percent by weight amounts to. Inhomogeneous mixtures are understood to be those which have a second have liquid or solid phase and, as a result, possibly a turbidity demonstrate.

The polar groups include the carbonamide and ester groups also free hydroxyl or amino or carboxyl groups, which are particularly important in the construction the polyester amides with a deficit or excess of acid components the alcoholic and basic components make a significant contribution can deliver. Below the percentage of polar groups is the total weight the -CONH-, -C00-, -OH-, -NH2 and -COOH radicals or groups in 100 parts by weight Understand polyester amide.

The polyester amides to be used can be obtained in a known manner from the the usual starting materials, such as polycarboxylic acids, hydroxycarboxylic acids, polyalcohols, Amino alcohols and polyamines. Among the polycarboxylic acids suitable for this purpose are preferably those which neither form cyclic anhydrides nor in a, ß-position to a carboxyl group lead to an olefinic double bond, such as z. B. adipic acid, pimelic acid, suberic acid, sebacic acid and decamethylene dicarboxylic acid, as well as dimerized and trimerized unsaturated fatty acids. As examples of Hydroxycarboxylic acids may be mentioned: lactic acid, 11-hydroxy-undecanoic acid, mono- and Dihydroxystearic acid and ricinoleic acid. These acids can be through the in the same Way reactive epoxy fatty acids, e.g. B. epoxidized oleic and linseed oil fatty acids, be replaced. As polyalcohols, for example: ethylene glycol, Butenediol, hexamethylene glycol, octadecanediol, glycerine, glycerine monooctyl ether, Trimethylolpropane, trimethylolpropane monobenzyl ether, pentaerythritol and pentaerythritol diallyl ether. Instead of the polyalcohols, epoxides and trimethylene oxide compounds that react like these can also be used, such as butadiene oxide, styrene oxide, glycide or 3-ethyl-3-methylol-trimethylene oxide, stepped be. As amino alcohols, for. B. ethanolamine, diethanolamine, propanolamine, 2-amino-3-heptanol, 7-aminoheptanol, 5-amino-4-octanol, N-dodecylmonoethanolamine and N-dodecyldiethanolamine to call. Examples of polyamines are ethylenediamine, tetramethylenediamine, hexamethylenediamine, 3-methylhexamethylenediamine, decamethylenediamine, 1-amino-3-methylaminopropane, N, N'-dimethylethylenediamine, Diethylenetriamine and triethylenetetraamine. Higher molecular weight Monocarboxylic acids, e.g. B. lauric acid, stearic acid, oleic acid, linseed oil fatty acid, as well as the fatty acids obtainable by paraffin oxidation have also been used. as well can be monohydric higher alcohols such as lauryl alcohol, stearyl alcohol, oleyl alcohol and pentaerythritol trinonyl ether to be condensed.

Such polyester amides are preferably used which are made using of polycarboxylic acids, polyamines with at least two primary amino groups and either Hydroxycarboxylic acids or polyalcohols or amino alcohols or mixtures of these Hydroxy compounds are made. The rest of the above components can also be used. Furthermore, among the polyester amides are the marked Kind of for the present litigation ones particularly suitable, whose polar group content is between about 14 and 30 percent by weight. That The ratio of the amide groups to the ester groups should preferably not be less than 0.1 and not greater than 2.2.

The softening point of the polyester amides used can vary within wide limits. Those polyesteramides whose softening point does not exceed 230 ° C. and in particular 200 ° C. are particularly suitable. The production of the polyester amides is not claimed here. The conditions for the combination according to the invention of the polyester amides with the ester binders depend both on the particular nature of the particular ester binder used and on the polyester amide, and ultimately also on the degree of thixotropy sought. The required proportions of polyester amide and ester binder can easily be determined in each case by means of a simple experiment. Good results are e.g. B. obtained when using such amounts of polyester amide that the end product contains 0.2 to 5.001 carbonamide groups.

The union of the ester binder with the polyester amides elevated temperature can take place both in the melt and in solution. Included can optionally esterification or transesterification, so z. B. Potassium Hydroxide, Sodium methylate, lithium stearate, calcium naphthenate and toluenesulfonic acid are added will.

In general, it is advisable to prevent atmospheric oxygen from entering to prevent implementation, e.g. B. by passing inert gases.

The reaction temperatures are expediently above the softening point of polyester amide; In general, however, it is not necessary to adjust the softening temperature of polyester amide to be exceeded significantly. The union of the ester binder with the polyester amide usually takes place in a satisfactory manner at temperatures from 100 to 240 ° C and in particular from 120 to 220 ° C.

In general, the polyester amides are incorporated into the Ester binder at significantly lower temperatures than the known conversion of polyamides based on polymerized fatty acids with binders of esters. As a result, the present method also enables the conversion such ester binders in thixotropic products that are very heat sensitive and tend to gelatinize at higher temperatures. Furthermore, the known implementation of the aforementioned polyamides with ester binders to a narrow temperature-time range bound, when exceeded the thixotropic properties of the product soon to be lost again. In contrast, stands for the union of the polyester amides with ester binders according to the invention a wide temperature-time range for Disposal. This makes the practical manufacture of the thixotropic products extraordinary relieved.

On the other hand, the new process claimed here means a considerable simplification compared to the process known from German Auslegeschrift 1 049 575 for the production of thixotropic urethane oils, in which transesterification products of triglycerides of drying or non-drying oils are reacted with polyalcohols with the hydroxyl groups present in equivalent or approximately equivalent amounts of diisocyanates , since the diisocyanates have to be obtained from the corresponding diamines, whereas in this case the use of diamines may be used directly to produce the polyesteramides and thus the thixotropic binders.

Such thixotropic ester binders are also used in the process according to the invention producible not only in solutions in aliphatic hydrocarbons, such as White spirit, show a pronounced thixotropic effect, but also in aromatic Hydrocarbons such as toluene, xylene, solvent naphtha or styrene, and if there is enough high amide group content, even in esters and ketones. With an additional addition from alcohols to the solutions mentioned one is able to increase the thixotropy set any lower degrees. In a mixture with non-thixotropic ester binders thixotropic properties are transferred to the mixture.

For the following examples, those in the table below were used characterized polyester amides (PEA) are used.

The test for inhomogeneity is expediently carried out in such a way that the mixture of 3 parts by weight of polyesteramide and 7 parts by weight of white spirit is heated to the boil and assessed after cooling to room temperature. Expand- Polar - CONH- Polvester mix of Components used to build up acid groups groups amid 3 parts PEA and in parts by weight number of points (PEA) weight- weight- 7 parts mineral spirits ° C percent percent Adipic Acid .......................... 146 insoluble A ricinoleic acid. . . . . . . . . . . . . . . . . . . . . . . . . 667 92 37 23.1 1l, 9 PEA insoluble Ethylenediamine. . . . . . . . . . . . . . . . . . . . . . . 66.6 heavily swollen Adipic acid .......................... 146 PEA insoluble, Castor oil ............................ 435 85 13.0 28.06 7.06 B glycol ........ 20.4 swollen Ethylenediamine ....................... 39.4 Adipic acid. . . . . . . . . . . . . . . . . . . . . . . . . . 146 two liquid C Castor oil .. ... . . . . . . . . . . ... . . . . . . . . . . 698 38 13.9 24.3 2.1 phases, the Ethylenediamine ....................... 12 lower cloudy Dimerized linseed oil fatty acid. . . . . . . . . . . . 556 PEA insoluble, D Glycol .............................. 32 108 11 15.06 7.4 swollen Ethylenediamine ....................... 30 Decamethylene dicarboxylic acid ........... 230 E Trimethylolpropane monobenzyl ether .... 179 142 12.5 22.2 5.4 # PEA insoluble Hexamethylene diamine. . . . . . . . . . . . . . . . . 29 Polester- Expanding- Polare -CONH- Components used to build up acid groups groups mixture of amide in parts by weight point number 3 parts PEA and (PEA) point weight i share white spirit o C percent percent Adipic acid .......................... 146 PEA insoluble, Linseed oil fatty acid ....................... 303 139 13.1. 27.68 9.25 F strong Trimethylol propane. . . . . . . . . . . . . . . . . . . . 101 swollen Hexamethylenediamine ... 58 Dimerized linseed oil fatty acid. . . . . . . . . . . . 556 two liquid G 1,3-butanediol ..................... ... 63 55 11 14.49 4.29 phases, the Ethylenediamine. . . . . . . . . . . . . . _. . . . . . 18 lower almost clear In the examples, the amounts are given in parts by weight. The viscosity data given to characterize the ester binders were determined in a DIN beaker (4 mm nozzle) at 20 ° C., unless otherwise stated. In all of the examples, the incorporation of the polyester amides into the ester binders was carried out while nitrogen was passed over them in order to prevent the ingress of atmospheric oxygen. Example 1 5 parts of the polyesteramide A are heated to 180 ° C. with 95 parts of an alkyd resin containing 51% linseed oil (acid number 9; viscosity f_40%) in white spirit: 75 seconds. The initially inhomogeneous mixture becomes clearly soluble in equal parts of xylene after 15 minutes at 180 ° C. It only becomes clearly soluble in white spirit after a boiling time of 4 hours at 180 ° C. On cooling to room temperature, the solutions solidify to form gel-like masses that are reversibly liquefied by stirring. The solutions siccativated with 0.020 /, cobalt, 0.30 /, lead and 0.020 /, manganese in the form of their naphthenates produce paint films which do not run off when applied to vertical surfaces and which are dust-dry after 3 hours. EXAMPLE 2 If 5 parts of polyesteramide A are heated with 95 parts of a linseed oil stand oil with a viscosity of 60 poises to 190 ° C., a reaction product which is clearly soluble in equal parts of xylene is obtained after 4 hours. The xylene solution, cooled to room temperature, forms a strongly thixotropic gel. After a further 7 hours of boiling time at a temperature increased to 215 ° C, the thixotropy is retained in 50% xylene solution, but the product is then also clear and thixotropically soluble in white spirit with the same mixing ratio. Example 3 10 parts of polyesteramide A are heated to 180 ° C. with 90 parts of an alkyd resin with a content of 650 % soybean oil (acid number 4; viscosity [50%] in white spirit: 53 seconds). After just one hour, a 50% solution of the reaction product that has become homogeneous in xylene is clear and thixotropic, while a product that is clear and thixotropically soluble in white spirit is only obtained after heating to 180 ° C. for a further 9 hours.

40 parts of a 50% solution after boiling for a total of 10 hours The product obtained in xylene at 180 ° C. is mixed with 60 parts of a 50% strength xylene solution of the soybean oil alkyd resin used for boiling is mixed at room temperature. Even this mixture still shows a very strong thixotropic effect. By stirring in 8% n-butanol in this mixture reduces the thixotropy somewhat, see above that the solution can be spread more easily and a better flow in the paint film results.

Example 4 10 parts of polyesteramide A are heated to 120 ° C. for 2 hours with 90 parts of an alkyd resin containing 40% coconut oil fatty acid (acid number 7; viscosity [50%] in xylene: 145 seconds) which is dissolved in 70 parts of xylene. After cooling to room temperature, the solution remains clear and shows strong thixotropy.

This heat-sensitive alkyd resin can be used at higher temperatures do not implement with the same certainty; so occurs z. B. at a boiling temperature from 220 to 230 ° C after a short time gelatinization.

100 parts of the thixotropic solution obtained at 120 ° C. have 44 Share an approximately 55% solution of a melamine formaldehyde resin in butanol, such as it is used in the paint industry to build up stoving enamels, at 60 ° C mixed. Even this mixture, which contains a lot of butanol, forms when it cools to room temperature a pronounced thixotropic gel that is easily liquefied by stirring.

Example 5 10 parts of polyesteramide A and 90 parts of a styrenated alkyd resin with a content of 350 % of drying oils and 45% polystyrene (acid number 7; viscosity [50%] in white spirit: 105 seconds) are heated to 180 ° C, after 3 hours a product which is clearly soluble in equal parts of xylene and which, on cooling, assumes an ointment-like consistency. Stirring gives a highly viscous solution whose thixotropic behavior can be weakened by adding alcohols to achieve better processing. Example 6 5 parts of the polyesteramide B and 95 parts of the alkyd resin used in Example 1 are heated to 180.degree. After 3 hours, the reaction product is clear and thixotropically soluble in xylene in a ratio of 1: 1. Example 7 The mixture of 50 parts of polyester amide C and 50 parts of an alkyd resin containing 630 % linseed oil (acid number 11; viscosity [50%] in white spirit: 53 seconds) is heated to 160 ° C. for 8 hours. The reaction product obtained in this way is dissolved in hot water both in white spirit and in xylene; in both cases, thixotropic solutions which remain clear and remain clear are obtained after cooling to room temperature.

Example 8 15 parts of polyester amide D and 85 parts of a 55111, linseed oil containing alkyd resin (acid number 7; viscosity [40 per cent] in White spirit: 71 seconds) are heated to 190 ° C. After 4 hours the reaction product is Clearly soluble in equal parts of white spirit. Solidifies on cooling to room temperature the solution to a non-flowing gel that can be liquefied by stirring. These properties of the reaction product are also retained when heating is extended to 25 hours at 190 ° C.

A more thixotropic reaction product is obtained if one 40 parts of the polyester amide with 60 parts of the alkyd resin heated to 210 ° C. for 7 hours. Example 9 10 parts of polyesteramide E are used with 90 parts of that used in Example 6 Alky dharzes heated to 180 ° C. The rapid implementation already delivers after 2 hours a homogeneous cooked product, which in xylene to a dilution of 30% is clear and thixotropically soluble. Example 10 10 parts of polyester amide F. and 90 parts of the alkyd resin used in Example 6 are heated to 190 ° C. After 1 hour, a sample remains clear after cooling to room temperature. The 50 per cent Solution of this product in xylene is strongly thixotropic. Example 11 A mixture of 50 parts of polyester amide G and 50 parts of the alkyd resin used in Example 7 is 6 hours at 160 ° C and then until it clears one to room temperature cooled sample heated to 180 ° C. The reaction product is 50% in white spirit solved. Over the course of 6 hours, the clear solution gradually solidified to a weak one thixotropic gel that can be easily liquefied by stirring.

Claims (4)

PATENT CLAIMS: 1. Process for the production of thixotropic lacquer binders based on esters such as fatty oils, alkyd resins, etc., by combining this with polyamides with heating, characterized in that ester binders combined in the heat with such polyester amides, their mixtures of 3 parts by weight Polyester amide and 7 parts by weight of mineral spirits are inhomogeneous at room temperature and their content of polar groups (total weight of -CONH-, -C00-, -OH-, -NH2 ; COOH residues or groups per 100 parts by weight of polyester amide) not more than 35 Weight percent, preferably between 14 and 30 percent by weight. 2. Procedure according to claim 1, characterized in that such polyester amides are used those using polycarboxylic acids, polyamines with at least two primary Amino groups and either hydroxycarboxylic acids or polyalcohols or amino alcohols or mixtures of these hydroxy compounds are prepared. 3. The method according to claim 1 and optionally 2, characterized in that the ratio of the amide groups to the ester groups in the polyester amides is between 0.1 and 2.2. 4. Procedure according to claim 1 and optionally 2 and 3, characterized in that the Mixture of paint binder and polyester amide at temperatures between 100 and 240 ° C, preferably between 120 and 220 ° C, heated.