DE102009056187A1 - Polyester resin obtained by polycondensation of mixture comprising polyol, polycarbonic acid, 2-propylheptanoic acid glycidyl ester and/or 4-methyl-2-propylheptanoic acid glycidyl ester, useful e.g. in coating composition - Google Patents

Abstract

Polyester resin (I), which is obtained by polycondensation of a mixture comprising (a) at least one polyol; (b) at least one polycarbonic acid or its derivative; (c) 2-propylheptanoic acid glycidyl ester and/or 4-methyl-2-propylheptanoic acid glycidyl ester, is claimed. Independent claims are included for: (1) coating agent comprising (I), at least one cellulose nitrate, and at least one polyisocyanate; and (2) aqueous coating composition comprising water soluble polyester resin having an acid number of 31-80 mg of potassium hydroxide/g.

Description

The The present invention relates to a polyester resin, and more particularly to a Alkyd resin, the 2-Propylheptansäureglycidester and / or Contains 4-methyl-2-propylhexanoic acid glycidyl ester incorporated, the use of these polyester resins as well as a coating agent, containing such a polyester resin.

alkyd resins are polyester resins, polybasic carboxylic acids, polyvalent ones Alcohols (polyols) and monocarboxylic acids incorporated. They are still one of the most important binder classes for the production of paints. Essential for their properties is the concomitant use of monocarboxylic acids in their preparation. Thus, the functionality of the polyols is reduced in situ, and it can be higher molecular weight products with tighter Molar mass distribution are obtained as in corresponding polyesters, used for their preparation no monocarboxylic acids become. By this Monocarbonsäuremodifikation leaves In general, a better solubility in usual Solvents, flexibilization of the resulting films and in the use of polyunsaturated monocarboxylic acids the Possibility to achieve oxidative crosslinking. The term "modified Alkyd resins "refers to synthetic resins, in addition to the constituents Polycarboxylic acid, polyol and monocarboxylic acid more Contain ingredients, for. Styrene, acrylates, polyamides, urethanes, Epoxies, silicones.

Alkyd resins are z. B. described in Rompp-Lexikon "Paints and printing inks", Georg-Thieme-Verlag, Stuttgart, 1998, p 20-22 ,

Monocarboxylic acids with secondary and especially with tertiary carboxyl groups Less or no in-situ reduction of functionality is appropriate the polyols. It is possible, however, in a pre-reaction a synthetic equivalent of polyol and monocarboxylic acid to produce, for. B. by the formation of glycidyl esters of such monocarboxylic acids. As building blocks of alkyd resins then react the glycidyl esters of Monocarboxylic acids with the polycarboxylic acids in one Addition reaction wherein an ester group and a free hydroxyl group are formed, the latter can be further esterified.

H. Wagner and HF Sarx describe in Lackkunstharze, 5th edition, Carl Hanser Verlag, Munich (1971), pp. 96-99 Among other things, the possibility of producing oil-free saturated alkyd resins from glycidyl esters of synthetic saturated carboxylic acids.

The US 6,277,497 describes a coating composition containing as binder a polyester polyol having end groups derived from a carboxylic acid having a tertiary carbon atom. The coating compositions are characterized by a low content of volatile organic compounds (VOC) with satisfactory viscosity properties. To prepare the polyester polyol, a polycarboxylic acid may be reacted with a glycidyl ester of the tertiary carbon carboxylic acid. Alternatively or additionally, a polycarboxylic acid may be esterified with epichlorohydrin and the resulting polyglycidyl ester derivative reacted with a carboxylic acid having a tertiary carbon atom or a derivative thereof.

The EP 1754 737 A1 describes polyester resins obtained by reacting (a) a polyol, (b) a polybasic carboxylic acid or anhydride thereof, and (c) a monoepoxide compound having a long chain hydrocarbon radical to a polyester polyol and further reacting with (d) a polybasic carboxylic acid or anhydride thereof and or (e) a polyisocyanate compound. They are suitable for water-based thermally curable coating compositions.

The not pre-published European patent application 07111275.9 describes C ₁₀ alkanoic acid glycidyl esters and their use for modifying low molecular weight and polymeric compounds such as polyacrylates. An application for the production of alkyd resins is not described.

It There is still a need for coating agents that possible low levels of volatile organic compounds (VOC) and especially solvents. This will be a reduction of the solution viscosity sought to the formulation of higher solids coating compositions to allow for the same viscosity.

The Task is solved by surprise Polyester resins based on 2-Propylheptansäureglycidesters and / or the 4-methyl-2-propylhexanoic acid glycidyl ester.

• a) wenigstens ein Polyol,
• b) wenigstens eine Polycarbonsäure oder ein Derivat davon, und
• c) wenigstens einen Glycidester, der ausgewählt ist unter 2-Propylheptansäureglycidester, 4-Methyl-2-propylhexansäureglycidester und Mischungen davon

enthält.A first subject of the invention is therefore a polyester resin A) which is obtainable by polycondensation of a mixture which

• a) at least one polyol,
• b) at least one polycarboxylic acid or a derivative thereof, and
• c) at least one glycidyl ester selected from 2-propylheptanoic acid glycidyl ester, 4-methyl-2-propylhexanoic acid glycidyl ester and mixtures thereof

contains.

• – Ihre Lösungen haben eine geringe Viskosität und ermöglichen die Formulierung von Beschichtungsmitteln mit höherem Feststoffgehalt bei gleicher Viskosität wie die aus dem Stand der Technik bekannten Beschichtungsmittel.
• – Durch das verbesserte Viskositätsverhalten bzw. die Möglichkeit von Formulierungen mit höheren Feststoffgehalten wird eine Reduktion der VOC-Werte bei der Applikation ermöglicht. Dies erfüllt eine wichtige aktuelle Anforderung des Lackmarktes nach umweltfreundlicheren Produkten.
• – Sie ermöglichen eine bessere Pigment- und/oder Untergrundbenetzung.
• – Beschichtungsmittel auf Basis der erfindungsgemäßen Polyesterharze verfügen über besseren Verlauf und/oder bessere Fülle.
• – Sie ermöglichen eine bessere Flexibilität der gehärteten Filme im Wesentlichen ohne reduzierte Oberflächenhärte.
• – Die gehärteten Filme zeichnen sich durch guten Glanz, Glanzerhalt und/oder Chemikalienbeständigkeit aus.

The polyester resins of the invention wei sen in addition to the usual properties for alkyd resins advantageous properties at least one of the following advantages:

• Their solutions have a low viscosity and allow the formulation of higher solids coating compositions of the same viscosity as the coating compositions known in the art.
• - Due to the improved viscosity behavior or the possibility of formulations with higher solids contents, a reduction of the VOC-values is possible in the application. This meets an important current requirement of the coatings market for more environmentally friendly products.
• - They allow a better pigment and / or substrate wetting.
• - Coating compositions based on the polyester resins according to the invention have better flow and / or better fullness.
• They allow better flexibility of the cured films substantially without reduced surface hardness.
• - The cured films are characterized by good gloss, gloss retention and / or chemical resistance.

at the polyols a) are polyhydric alcohols which are at least have two, preferably at least three OH groups. Preferably contains the component a) at least one higher-functional polyol, which has at least three OH groups. Suitable higher functional Polyols are preferably selected from trimethylolpropane (TMP), trimethylolethane (TME), glycerol, pentaerythritol, sugar alcohols, Ditrimethylolpropane, dipentaerythritol, diglycerol, trishydroxyethyl isocyanurate and mixtures thereof. In a special embodiment If component a) consists only of higher functional polyols. In another specific embodiment the component a) at least one higher-functional polyol and at least one diol. Suitable diols are z. B. selected under Ethylene glycol, propylene glycol, butanediol-1,4, pentanediol-1,5, hexanediol-1,6, Neopentyl glycol, 2-butyl-2-ethylpropanediol-1,3, diethylene glycol, Dipropylene glycol, higher polyether diols, dimethylol cyclohexane, and mixtures thereof.

suitable Compounds b) are polybasic carboxylic acids or their Anhydrides, such as phthalic acid, phthalic anhydride, Isophthalic acid, terephthalic acid, trimellitic acid, Trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, Tetrahydrophthalic acid, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, tricyclodecanedicarboxylic acid, Succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, Sebacic acid, maleic acid, maleic anhydride, Fumaric acid, itaconic acid, mesaconic acid, Citraconic acid, dimer fatty acids and mixtures from that. In a preferred embodiment, the component is b) exclusively selected among polycarboxylic acids the following class 1.

In Another preferred embodiment is the Component b) to at least 50 wt .-%, based on their total weight, of at least one polycarboxylic acid of the following class 1. According to this embodiment, component b) not more than 50% by weight, relative to their total weight, of at least one polycarboxylic acid of the following class 2. According to this embodiment, the component b) in addition at least one class 1 polycarboxylic acid and optionally at least one class 2 polycarboxylic acid, in addition still up to at most 10% by weight of at least one polycarboxylic acid Class 3.

class 1: phthalic acid, phthalic anhydride, isophthalic acid, Terephthalic acid, trimellitic acid, trimellitic anhydride, Pyromellitic acid, pyromellitic dianhydride, Tetrahydrophthalic acid, tetrahydrophthalic anhydride, Hexahydrophthalic acid, hexahydrophthalic anhydride and mixtures thereof.

class 2: succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, Dimer fatty acids and mixtures thereof.

class 3: maleic acid, maleic anhydride, fumaric acid, Itaconic acid, mesaconic acid, citraconic acid and mixtures thereof.

4-Methyl-2-propylhexansäureglycidester der Formel

oder einem Gemisch der beiden.The glycidic esters of component c) are selected from 2-Propylheptansäureglycidester of the formula

4-Methyl-2-propylhexanoic acid glycidyl ester of the formula

or a mixture of the two.

In a first specific embodiment, component c) consists exclusively of 2-propylheptanoic acid glycidyl ester. In a second specific embodiment, component c) comprises a mixture from 2-Propylheptansäureglycidester and 4-methyl-2-propylhexansäureglycidester.

2-Propylheptansäureglycidester, 4-methyl-2-propylhexansäureglycidester or a mixture of the two can be easily obtained by dimerization of pentenes and subsequent oxidation, as described in the DE-A-102 39 134 is described. The dimerization of the penteno generally produces a mixture of 2-propylheptene and 4-methyl-2-propylhexene. The mixture can be worked up and the pure compounds can then be oxidized to the carboxylic acids and used further. However, it is also possible to oxidize the mixture without separation of the alkenes to the corresponding carboxylic acid mixture. Optionally, a separation of the carboxylic acid mixture can then follow. However, separation of the dimerization products of the penteno or of the carboxylic acids is in many cases not necessary, since the glycidic esters of both carboxylic acids are suitable for use in the context of this invention.

at the production of carboxylic acids by dimerization of Pentenes and subsequent oxidation can be more By-products arise, for. For example, formic acid esters such as 1-propyl hexyl formate or formic acid 3-methyl-1-propyl-pentyl ester, nonanol, 6-methyl-octan-4-ol formic acid, etc., and mixtures thereof. For many applications, there is a separation of these by-products not before the preparation and further use of the glycidyl esters necessary.

Preferably contain at most the glycidic ester used as component c) 20 wt .-%, particularly preferably at most 10 wt .-%, in particular at most 5 wt .-% by-products, based on the total weight from 2-Propylheptansäureglycidester, 4-methyl-2-propylhexansäureglycidester and by-products.

If a mixture of 2-propylheptanoic acid and 4-methyl-2-propylhexanoic acid glycidyl ester is used as component c), this contains, for example
1 to 99 wt .-% 2-Propylheptansäureglycidester and
1 to 99% by weight of 4-methyl-2-propylhexanoic acid glycidyl ester,
where the percentage is based on the sum of the two.

Particularly preferably, the mixture consists of
10 to 90 wt .-%, in particular 20 to 80, wt .-%, 2-Propylheptansäureglycidester and
10 to 90 wt .-%, in particular 20 to 80 wt .-%, 4-methyl-2-propylhexansäureglycidester.

to Preparation of the polyester resins according to the invention the compounds of component c) are preferably in one Amount of 5 to 75 wt .-%, preferably 10 to 50 wt .-%, based on the Total weight of the components used for the polycondensation (i.e., components a) to e)).

to Preparation of the glycidic esters used according to the invention c) the following methods are considered, to which reference is made in full.

The DE-A-2 107 084 describes a process of transesterification of carboxylic acid methyl ester with glycidyl acetate or propionate with sodium methylate or ammonium hydroxide as catalysts; the resulting methyl acetate is distilled off.

The DE-A-24 46 944 describes a reaction of carboxylic acid with a boiling mixture of epichlorohydrin (2.5-fold molar excess) and sodium carbonate (0.5 mol with respect to the acid). In the water separator separate water of reaction and epichlorohydrin. Epichlorohydrin is recycled. When all the water has been removed, the addition of triethylbenzylammonium chloride, then it is stirred at 110 to 115 ° C and worked up by filtration (NaCl) by distillation.

Another method is the esterification of carboxylic acids with glycidol with carbodiimides (eg DCC) as acylating reagents and pyridines (eg DMAP) as catalysts according to EP-A-0697018 , Urea is filtered off, the catalyst is removed with an acidic ion exchanger.

The US 5,036,154 describes the sodium tungstate-catalyzed epoxidation of allyl esters with 70% H ₂ O ₂ . It is a 2-phase reaction (water / toluene) with trioctylammonium chloride as a phase transfer catalyst.

The EP 1115714 describes the reaction of neodecanoic acid with an approximately 4-fold molar excess of epichlorohydrin in the presence of isopropanol (water-miscible alcohol), water and NaOH.

According to WO 00/44836 is prepared from 1 mole of 2-ethylhexanoic acid and 2 moles of NaOH, the Na salt of the acid in toluene. Forming water is distilled off azeotropically with the aid of toluene. At 50 ° C, 3 moles of epichlorohydrin are slowly added. The mixture is heated to reflux. After the end of the reaction, the epichlorohydrin is distilled off and the product is distilled under reduced pressure.

• a) 2-Propylheptansäure, 4-Methyl-2-propylhexansäure oder deren Gemische werden mit Epichlorhydrin in Gegenwart eines Chromsalzes umgesetzt,
• b) die erhaltene Hydroxyverbindung wird in Gegenwart eines Alkali- oder Erdalkalihydroxids zum Glycidester umgesetzt, und
• c) das erhaltene Gemisch wird anschließend gegebenenfalls extraktiv aufgearbeitet.

Another suitable process for preparing the glycidyl esters used as component c) comprises the following process steps a) to c):

• a) 2-propylheptanoic acid, 4-methyl-2-propylhexanoic acid or mixtures thereof are reacted with epichlorohydrin in the presence of a chromium salt,
• b) the resulting hydroxy compound is reacted in the presence of an alkali or alkaline earth metal hydroxide to the glycidyl ester, and
• c) the resulting mixture is then optionally worked up by extraction.

in the Process step a) is epichlorohydrin preferably in amounts from 0.9 to 2 mol, more preferably in amounts of from 1 to 1.5 mol, used based on 1 mole of alkanecarboxylic acid. For the chromium salt it can be any salt of chromium (II) or chromium (III) In particular, carboxylic acid salts are suitable (Alkanoates), e.g. As chromium (II) acetate or chromium (II) ethylhexanoate or chromium (II) hydroxides or mixed anions (hydroxide and alkanoate). The chromium salt is preferably in amounts of 0.0001 to 0.01 mol, particularly preferred from 0.0005 to 0.005 mol, based on 1 mol of alkanecarboxylic acid, used. The reaction in process step a) is preferably at normal pressure (1 bar) and at a temperature of 30 to 100 ° C, preferably 60 to 90 ° C, performed. In the Implementation, a solvent can be used; in general but a solvent is not required. The implementation in process step a) is preferably monitored by gas chromatography; Preferably, a complete reaction of the alkanecarboxylic acid takes place to the hydroxy compound. Process step b) closes preferably directly to process step a) without a workup after completion of the reaction in step a) takes place. at the alkali or alkaline earth metal hydroxide may be any Hydroxide, preferably an alkali hydroxide, such as NaOH or KOH, act. The alkali or alkaline earth metal hydroxide is preferably used in Amounts of 1 to 2 mol, based on 1 mol of the process step a) obtained hydroxy compound, used, the molar amount corresponds preferably the amount of alkanecarboxylic acid used, since in process step a) preferably a complete Implementation takes place. The reaction in process step b) is preferably also at normal pressure (1 bar) and at a temperature of 30 to 100 ° C, preferably 30 to 80 ° C performed. The dropping rate is preferably chosen that the temperature remains in the selected range after completion of the Addition of the alkali or alkaline earth metal hydroxide is preferably still some time, z. B. two hours, stirred. A checkpoint the reaction can preferably be carried out by gas chromatography. Then done preferably an extractive workup of the after process step b) the mixture obtained. Particularly preferred is an extractive Work-up with water. The resulting aqueous phase and organic Phase are separated and the organic phase dried, preferably by adding a desiccant such as sodium sulfate. The glycidyl esters or mixtures thereof can in this process in large Purity and yield are obtained.

In a special embodiment, that for the production of used according to the invention polyester resins mixture additionally as component d) at least one hydroxycarboxylic acid or a derivative thereof. The compounds of component d) differ itself from the polycarboxylic acids b). Suitable z. Ε-caprolactone, hydroxypivalic acid, dimethylolpropionic acid, Ricinol fatty acid, hydroxystearic acid and mixtures from that.

to Preparation of the polyester resins according to the invention A), the compounds of component d) are preferably in one Amount of from 0 to 50% by weight, particularly preferably 0 to 25% by weight, in particular 0 to 10 wt .-%, based on the total weight of components used for polycondensation (i.e., components a) to e)) are used. If the component d) is used, then z. B. in an amount of 0.5 to 50 wt .-%, preferably 1 to 25 wt .-%, in particular 1.5 to 10 wt .-%, based on the total weight of components used for polycondensation (i.e., components a) to e)).

In a specific embodiment, the mixture used to prepare the polyester resins according to the invention additionally comprises, as component e), at least one monocarboxylic acid or a derivative thereof which is different from component c). These include, in general, saturated or monounsaturated or polyunsaturated monocarboxylic acids. The monocarboxylic acids may have linear, alicyclic or aromatic hydrocarbon radicals. Preference is given to C ₈ - to C ₃₂ -monocarboxylic acids, especially C ₁₀ - to C ₂₂ -monocarboxylic acids.

Suitable as component e) are z. B. naturally occurring fatty acids, which are present as oils or fats in the form of triglycerides. You can for the preparation of the invention Polyester resins by polycondensation in the form of the free fatty acid or a derivative, especially in the form of a triglyceride used become. Such fatty acid derivatives are accordingly also called oil component. Examples of oil components are drying oils (such as linseed oil), semi-drying oils (like soy oil) and non-drying oils (like castor oil).

Suitable as component e) are synthetic long-chain monocarboxylic acids, cyclic monocarboxylic acids, resin acids, Koch's acid (Versatic ^® acid), etc.

The compounds of component e) are preferably selected from fatty acids of linseed oil, soybean oil, cottonseed oil, sunflower oil, safflower oil, castor oil, fish oils, coconut fat, palm kernel oil, rapeseed oil, oiticica oil, wood oil, ricinole oil, tall oil, and derivatives and mixtures thereof. Suitable derivatives are the mono-, di- and especially triglycerides. The compounds of component e) are preferably selected from pelargonic acid, isooctanoic acid, isononanoic acid, benzoic acid, tert.-butylbenzoic acid, abietic acid, levopimaric acid, Versatic ^® acid and mixtures thereof.

to Preparation of the polyester resins according to the invention A), the compounds of component e) are preferably in one Amount of 0 to 50 mol%, particularly preferably 0 to 25 mol%, in particular 0 to 10 mol%, based on moles OH groups of the polyol component a). If the component e) is used, then z. In an amount of 0.5 to 50 mol%, preferably 1 to 25 mol%, in particular from 1.5 to 10 mol%, based on moles of OH groups of the polyol component a).

The preparation of the polyester resins A) according to the invention can be carried out by polycondensation (esterification) in a conventional manner. Suitable methods are for. In Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie Weinheim, 4th edition (1980), Volume 19, pages 61 et seq. or in H. Wagner and HF Sarx, "Lackkunstharze", Carl Hanser Verlag, Munich (1971), pages 86-152 , described in detail.

The Polycondensation is preferably carried out in the presence of an inert gas, z. As nitrogen, helium or argon.

The Polycondensation may optionally be carried out in the presence of a catalytic Made amount of a conventional esterification catalyst. These include z. As acids, bases, salts thereof or transition metal compounds. Suitable as esterification catalysts are phosphorus (I) compounds, such as Phosphinic acid (hypophosphorous acid) or salts phosphoric (I) acid (phosphinates, hypophosphites). Suitable titanates are also preferred as esterification catalysts Tetraalkylorthotitanates, in particular tetraisopropyl titanate and Tetrabutyl titanate.

The Polycondensation is preferably carried out at a temperature in the range from about 100 to 300 ° C, more preferably in the range from 120 to 260 ° C.

In a special embodiment, the polycondensation takes place in the sense of a melt condensation. The melt condensation can take place in one or more stages, preferably a single-stage melt condensation. Under one-step is understood that all for the production components used in the polyester resin a) to c) and, if present, d) and / or e) are already present at the beginning of the polycondensation. This includes processes in which the reaction z. B. under continuous or stepwise increase in temperature he follows.

At the Use of carboxylic anhydrides in the polycondensation (such as phthalic anhydride, maleic anhydride, etc. as component b)), the reaction is preferably carried out under Gradual increase in temperature in the course of polycondensation. After this execution, at least first a part of the glycidyl esters of component c) and at least one part the anhydrides b) reacted in an addition reaction with each other. The reaction then takes place initially preferably at a Temperature in a range of about 100 to 180 ° C. Consequently is an uncontrolled reaction due to the exothermic Addition reaction avoided resulting heat of reaction. The further reaction is then carried out with heating to a Temperature of about 180 to 300 ° C, more preferably 180 to 260 ° C, with elimination of water.

Preferably For the melt condensation, an entrainer, such as toluene or Xylene, used. The amount of the entraining agent is then preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on the total weight of the melt condensation used component a) to e).

The Control of the hydroxyl number and the acid number of the invention Polyester resins can by the nature of the reactants used (especially their hydroxyl and carboxylic acid equivalents), the stoichiometry of the educts used and / or the reaction time the polycondensation take place. So usually the polycondensation so long under analytical control, until the desired values for the hydroxyl and acid number are reached. The molecular weight of the invention Polyester resins can analytically, z. B. by GPC.

The Polyester polyols according to the invention are in general solid, colorless or slightly colored, clear resins. she are generally in inert paint solvents such as Hydrocarbons, such as toluene, xylene, solvent naphtha, or higher alkylbenzenes; Esters such as ethyl acetate, butyl acetate, ethoxypropyl acetate, ethoxyethyl; Ketones such as methyl ethyl ketone or methyl isobutyl ketone or mixtures of two or more than two of these paint solvents soluble.

The viscosities of polyesters, especially in the form of solutions in a suitable solution medium (solution viscosity), are generally influenced in addition to the components used for their preparation of the average molecular weight and the degree of branching. The solution viscosities of the polyesters A) according to the invention are significantly lower than those of polyesters of comparable building blocks, comparable average molecular weight and comparable degree of branching but without glycidic ester. This results in the possibility of producing particularly solids-rich lacquers with the polyesters A) according to the invention. Surprisingly, polyesters based on the 2-propylheptanoic acid glycidyl ester and / or 4-methyl-2-propylhexanoic acid glycidyl ester also have lower viscosities in comparison to those prepared from the known glycidyl ester of neodecanoic acid (see Examples and Comparative Examples). This difference is particularly significant when using relatively non-polar solvents such as hydrocarbons. Hydrocarbons are preferred among others because they are less expensive than other solvents.

The polyester resins according to the invention preferably have z. B. as a 70% solution in Aromatic 100 (aromatic solvent having a boiling range of 158 to 172 ° C at 1013 hPa) a viscosity of 400 to 20,000 mPas, particularly preferably from 400 to 4000 mPas, determined by ISO 291 at 23 ° C in a cone-and-plate viscometer, on.

The Polyester resins according to the invention preferably have a number average molecular weight of 550 to 10,000 g / mol.

The polyester resins according to the invention preferably have an iodine color number (determined after DIN 6162 ) of at most 20, more preferably of at most 15.

The polyester resins according to the invention preferably have an OH number (determined after DIN 53240 ) in the range of 5 to 300 mg KOH / g, more preferably from 10 to 180 mg KOH / g. Polyester resins of the invention, which are used in combination with at least one crosslinker which is capable of reacting with OH groups, preferably have an OH number (determined according to DIN 53240 ) in the range from 70 to 300 mg KOH / g, more preferably from 75 to 180 mg KOH / g, especially from 80 to 150 mg KOH / g.

The polyester resins of the invention preferably have an acid number (determined after DIN 53402 . ISO 2114 ) in the range of 0 to 80 mg KOH / g, more preferably from 5 to 70 mg KOH / g. Polyester resins according to the invention, which are used in coating compositions which comprise at least one organic solvent, preferably have an acid number (determined by DIN 53402 . ISO 2114 ) in the range of 0 to 30 mg KOH / g, more preferably from 0 to 25 mg KOH / g. Polyester resins according to the invention, which are used in water-dilutable coating compositions, preferably have an acid number (determined after DIN 53402 . ISO 2114 ) in the range of 31 to 80 mg KOH / g, more preferably from 35 to 70 mg KOH / g, especially from 40 to 65 mg KOH / g.

One Another object of the invention is a coating composition, the at least one polyester resin A) as defined above.

The Coating compositions according to the invention can both exclusively by physical drying as also in addition to form films by networking. The invention Coating agents can thus be used in physically drying, self-crosslinking or crosslinkable form. That is, the coating agent at least one polyester resin A) and optionally at least one Another binder containing physically drying, self-crosslinking or are networkable. It is also possible to use several binders, the different ways coating films form or cure / crosslink.

In the coating compositions of the invention can the polyester resins A) in combination with at least one other Be contained paint component. These include binder components B), who are capable of filming themselves or together with the polyester resins A) film. The binder component B) is preferably selected from among the polyester resins A) various polymeric binders, crosslinking agents, from Crosslinking agents different reactive diluents and Mixtures thereof.

In the case of physically drying coating compositions, the binder forms a polymer film during drying, without appreciable crosslinking of the polymer chains occurring among one another. In self-crosslinking coating compositions, the polymer chains of the binder have complementary functional groups capable of reacting with each other to form bonds, ie, crosslink. The self-crosslinking takes place during the drying of the coating, optionally by the action of elevated temperatures and / or by actinic radiation. In crosslinkable coating compositions, the polymer chains of the binder have functional groups that are complementary to the functional groups of a crosslinking agent. Binders and crosslinking agents are then able to crosslink with each other through a covalent interaction (ie, forming covalent bonds) or non-covalent interaction (ie, ionic interaction such as salt formation). Binders, which with actinic radiation (z. B. UV radiation) are crosslinkable or thermally crosslinkable, have functional groups which react with a crosslinking agent using actinic radiation or elevated temperature to form bonds and thus cause crosslinking. Binders which crosslink by combined use of actinic radiation and heat are also referred to as dual-cure binders. Polymeric binders suitable as binder component B) generally have a higher molecular weight than crosslinking agents and reactive diluents. The number average molecular weight of the polymeric binders is typically in the range of 500 to 2,000,000 daltons, such as 500 to 1,000,000 daltons, especially 1,000 to 100,000 daltons.

For only physically drying coating agents are the others Binder B), which - with sufficient compatibility - with the polyesters A) according to the invention combined be, preferably higher molecular weight polymers from the polymer classes the cellulose ester, such as cellulose acetate, cellulose acetobutyrate, Cellulose nitrate; Polyvinyl compounds, such as polyvinyl esters, polyvinyl ethers, Polyvinyl acetals, PVC and its copolymers; fluorochemical Polymers and their copolymers; Rubber derivatives such as cyclo rubber and chlorinated rubber, and polystyrene and its copolymers. It It is also possible to use mixtures of the abovementioned binders B) become. The only physically drying coating compositions can contain further binder components, such as aldehyde resins, ketone resins and xylene-formaldehyde resins. The invention Polyester A) contribute to plasticization in these combinations, Pigment wetting, raising the processing solids, Improvement of course and shine.

For crosslinkable coating compositions are the further binders B) preferably those with the remaining hydroxyl groups and optionally present carboxyl groups of the invention Polyester A) can react. Such crosslinkers are z. B. amino resins such as melamine resins, urea resins, benzoguanamine resins, Carbamate resins, glycolurils; or polyisocyanate adducts with free Isocyanate groups or capped isocyanate groups; Phenolic resins, like resoles; epoxy resins; reactive siloxanes with hydroxyl or alkoxyl groups; polymeric titanic acid esters. The networking can occur at room temperature, which is the formulation of two-component paint systems requires, or at a higher temperature and / or by the Influence of catalysts.

The polyesters A) according to the invention can, as mentioned, also be combined in coating compositions with other binders B), which in turn can crosslink. Such binders may be self-crosslinking if they contain complementary reactive groups, or if due to a content of reactive unsaturated groups due to higher temperature or due to the influence of actinic radiation z. B. crosslink UV radiation. Such self-crosslinking systems also include polymers which have ethylenically unsaturated double bonds. Such polymers are known in the art, for. B. off PKT Oldring (Editor), Chemistry and Technology of UV and EB Formulations for Coatings and Paints, Vol. II, SITA Technology, London, 1991, pp. 37-206 , as well as from the literature cited therein and commercially available. These are z. For example, polyether (meth) acrylates, polyester (meth) acrylates, urethane (meth) acrylates, silicone (meth) acrylates, epoxy (meth) acrylates, melamine (meth) acrylates, (meth) acrylate-modified polyurethanes and (meth) acrylate-modified copolymers based on (meth) acrylic acid esters.

crosslinkable but further binders B) can also be used with the abovementioned Crosslinkers for the invention Polyester A) and then react together with these and film. Such binders are z. As other polyesters, alkyd har ze, Acrylate resins, epoxy resins, epoxy esters, polyurethanes, polyethers, partially hydrolyzed polyvinyl esters, PVC copolymers, styrene copolymers, the all contain corresponding reactive groups.

Furthermore is it possible with the invention Polyesters A) and other crosslinkable binders B) different To carry out crosslinking reactions in the filming. As mentioned, z. B. binder combinations under combined Application of heat and actinic radiation as dual-cure systems designated.

If the inventive polyesters A) sufficient Proportions of polyunsaturated fatty acids the Component e) can thus oxidatively crosslinking Coating materials are produced. The oxidative crosslinking takes place at ambient temperature or at elevated temperature and is catalyzed by driers. Such binders may contain other binders B) as combination partners, such as As other oxidatively crosslinking alkyd resins, epoxy esters with unsaturated fatty acids, natural resins, modified Natural resins, resin-modified phenolic resins, called drying oils and modified oils and rubber derivatives.

However, the polyesters A) according to the invention can also be building blocks for further binders:
The polyesters A) according to the invention can form segments in polyurethanes and polyureas by reacting with polyisocyanates, which further optionally react with polyols and / or polyamines, resulting in binders for coating agent. These polyurethanes and polyureas may preferably form films by physical drying, but there are also crosslinking products. In a particular embodiment, such polyurethanes or polyureas are water-dilutable.

The Polyester A) according to the invention can on their excess hydroxyl groups or carboxyl groups with acrylic acid or methacrylic acid as well their derivatives (anhydrides) or their esters, in particular the Hydroxyalkyl esters are reacted. It is also possible, from the polyesters A) according to the invention together with hydroxyalkyl (meth) acrylates or hydroxyalkyl vinyl ethers and Polyisocyanates Polyurethanes with unsaturated groups manufacture. These polyester (meth) acrylates or polyurethane (meth) acrylates can by the influence of temperature or actinic radiation (UV radiation) crosslink using suitable initiators and accelerators.

Such binders are combined with reactive diluents. Reactive diluents are low molecular weight, liquid compounds which have at least one polymerizable, ethylenically unsaturated double bond. An overview of reactive diluents can be found z. In JP Fouassier (ed.), Radiation Curing in Polymer Science and Technology, Elsevier Science Publisher Ltd., 1993, Vol. 1, pp. 237-240 , Examples of such reactive diluents are acrylic acid esters such as butanediol diacrylate, hexanediol diacrylate, octanediol diacrylate, decanediol diacrylate, cyclohexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta / hexaacrylate, dipropylene glycol diacrylate and the corresponding esters of methacrylic acid and LR 8887 products sold under the Laromer ^® brands of BASF SE. PO 33F, LR 8967 and LR 8982. Other reactive diluents are also vinyl ethers such. B. butanediol mono- and divinyl ether, cyclohexyl vinyl ether, divinyl ether of di- and triethylene glycol and vinyl esters such. B. adipic acid divinyl ester. Reactive diluents initially act as solvents for achieving a favorable processing viscosity. But since they then react together with the binder and form the film, solvent emissions are largely avoided. The polyesters A) according to the invention contribute to the improvement of compatibility, solubility, wetting, adhesion, flow and gloss in such systems.

The Coating compositions according to the invention can in addition to at least one polyester resin A) and optionally at least one binder component B) at least one Additive C).

The Additives C) are preferably selected from pigments, Dyes, nanoparticles, fillers, leveling agents, Plasticisers, biocides, defoamers, antioxidants, UV stabilizers, Slip additives, emulsifiers, protective colloids, wetting agents, deaerating agents, film-forming auxiliaries, adhesion promoters, crosslinking catalysts, Photoinitiators, radical-forming initiators, polymerization inhibitors, Corrosion inhibitors, rheology-modifying additives, antifreeze agents, Flame retardants, etc. and mixtures thereof. They are each contained in the typical quantities.

The Coating agent according to the invention can be at least a pigment as additive C). Suitable are in principle inorganic pigments, organic pigments and mixtures thereof. The pigments may be coloring pigments, effect-giving Pigments, transparent pigments or mixtures thereof.

suitable inorganic pigments are z. B. white pigments such as titanium dioxide, preferably in the rutile form, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopone (zinc sulfide + Barium sulfate) or colored pigments, for example iron oxides, Carbon black, graphite, zinc yellow, zinc green, ultramarine, Manganese black, antimony black, manganese violet, Parisian blue or Schweinfurter green. Suitable organic color pigments can from different classes of dyes with different chromophores For example, anthraquinone dyes, monoazo and diazo dyes, Indigo and indigoid dyes, quinophthalones, methine and azamethine dyes, naphthalimide dyes, Naphthoquinone dyes, nitro dyes, quinacridone, phthalocyanine, Isoindolinone and metal complex pigments, etc. Examples of suitable organic coloring pigments C) are indanthrene blue, chromophthal red, Irgazine orange and Heliogen green.

As effect pigments C) metal flake pigments such as commercial aluminum bronzes according to DE-A-36 36 183 , chromated aluminum bronzes and commercial stainless steel bronzes and non-metallic effect pigments, such. As pearlescent or interference pigments used. Also suitable are synthetic white pigments with air inclusions to increase the light scattering as the Rhopaque ^® dispersions. Further examples of suitable effect pigments are expected Römpp Lexicon, paints and printing inks, Georg Thieme Verlag, 1998, page 176 , forth.

The proportion of pigments C) on the coating agent can vary very widely. Advantageously, the proportion is 1 to 95 wt .-%, preferably 2 to 90 wt .-%, particularly preferably 3 to 85 wt .-% and in particular 4 to 80 wt .-%, each based on the total solids content of the coating composition of the invention.

The Coating composition according to the invention can be used as Additive C) also contain at least one dye. there can it be z. B. for usual molecular emulsions soluble dyes or solvent dye act.

Suitable fillers C) are organic and inorganic fillers, for. As aluminosilicates such as feldspars, silicates such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth sulfates such as calcium sulfate, silica, etc. Suitable organic fillers are, for. As textile fibers, cellulose fibers, polyethylene fibers or wood flour. In paints finely divided fillers are naturally preferred. The fillers can be used as individual components. In practice, filler mixtures have proven particularly useful, for. As calcium carbonate / kaolin, calcium carbonate / talc. In addition, it will open Römpp Lexikon, paints and printing inks, Georg Thieme Verlag, 1998, pages 250 ff. , "Fillers", directed.

Of the Proportion of the fillers C) is on the coating agent preferably 0 to 95% by weight, particularly preferably 0.5 to 90% by weight, in particular from 1 to 75% by weight and especially from 4 to 80% by weight, in each case based on the total solids content of the invention Coating agent.

Suitable flow control agents are for. B. modified silicone oils such as the Byk ^® brands Altans-Byk or high molecular weight polyacrylates, such as the Resiflow ^® brands Worlée.

When Additive C) are suitable UV stabilizers (light stabilizers) z. 4, 4-diarylbutadienes, cinnamic acid esters, triazoles, triazines, Benzophenones, diphenyl cyanoacrylates, oxamides (oxalic acid diamides), oxanilides, etc. Suitable sterically hindered amines are, for. For example, 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or their derivatives, e.g. B. bis (2,2,6,6-tetramethyl-4-piperidyl) sebacinate. UV stabilizers, are usually used in an amount of 0.1 to 5.0% by weight. and preferably from 0.5 to 3.5% by weight, based on the total weight of the Coating agent used.

The Coating composition according to the invention can be used as Additive C) also contain at least one emulsifier. Suitable are in principle anionic, nonionic and cationic emulsifiers. Suitable and preferred emulsifiers are hereinafter aqueous Coating agents described in more detail, to which reference is made here is taken. If the coating compositions of the invention contain at least one emulsifier, their proportion is usually 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the Total weight of the coating agent.

The Coating composition according to the invention can be used as Additive C) also contain at least one protective colloid. suitable Protective colloids are hereafter in aqueous coating compositions described in more detail, to which reference is made here.

suitable Wetting agent C) are z. B. siloxanes, fluorine-containing compounds, carboxylic acid monoesters, phosphoric acid esters, Polyacrylic acids and their copolymers or polyurethanes.

suitable film-forming aids C) are z. B. cellulose derivatives.

self- or crosslinkable coating agents can be used as auxiliaries C) contain at least one catalyst which the respective Crosslinking reaction promotes (crosslinking catalyst). To count z. For example, acids such as p-toluenesulfonic acid, Methanesulfonic acid, sulfuric acid, phosphoric acid and the salts thereof, such as. As the ammonium salts. Typical catalysts for coating compositions containing at least one polyisocyanate are organotin compounds, such as dibutyltin dilaurate, Dibutyltin oxide, tin octoate, and tertiary amines and their Ammonium salts, such as triethylamine, dimethylbenzylamine, dimethylethanolamine, benzoyltrimethylammonium hydroxide, Tetrabutylammonium iodide, etc.

crosslinking catalysts C) are usually used in an amount of from 0.01 to 5% by weight, preferably 0.05 to 1 wt .-%, based on the total weight of the coating agent used.

UV-curable coating compositions generally contain 0.01 to 5 wt .-%, preferably 0.1 to 2 wt .-% of at least one photoinitiator C), which can initiate the polymerization of ethylenically unsaturated double bonds. These include z. Benzophenone and benzophenone derivatives such as 4-phenylbenzophenone and 4-chlorobenzophenone, Michler's ketone, anthrone, acetophenone derivatives such as 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone , Benzoin and benzoin ethers such as methyl, ethyl and butyl benzoin ethers, benzil ketals such as benzil dimethyl ketal, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, anthraquinone and its derivatives such as ( Methylanthraquinone and tert-butylanthraquinone, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate and bisacylphosphine oxides Such initiators are, for example, those commercially available ter the trademarks Irgacure ^® 184, Darocure ^® 1173 products of Ciba Geigy, Genocure ^® from Rahn or Lucirin ^® TPO from BASF SE available.

coating agents based on polymers which have ethylenically unsaturated double bonds, can as additive C) at least one radical-forming Initiator contained in the exposure to elevated temperature a polymerization of these groups and thus a radical crosslinking causes. These include thermolabile radical initiators, such as organic peroxides, organic azo compounds or C-C-cleaving Initiators such as dialkyl peroxides, peroxycarboxylic acids, peroxodicarbonates, Peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.

The coating composition according to the invention may also contain as additive C) at least one rheology-controlling additive. Suitable rheology-controlling additives are, for. In WO 94/22968 . EP-A-0 276 501 . EP-A-0 249 201 or WO 97/12945 described. Also suitable are crosslinked polymeric microparticles, as used for example in the EP-A-0 008 127 are disclosed; inorganic phyllosilicates, preferably smectites, in particular montmorillonites and hectorites, such as aluminum-magnesium silicates, sodium magnesium and sodium magnesium fluorine lithium phyllosilicates of the montmorillonite type, silicas such as aerosils, or synthetic polymers with ionic and / or associative acting groups such as polyvinyl alcohol, poly (meth) acrylamide, crosslinked poly (meth) acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified polyacrylates; or associative thickeners based on polyurethane, as described in Römpp Lexikon, Paints and Printing Inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Thickening Agents", pp. 599-600 , and in the textbook "Paint Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pp. 51-59 and 65 , to be discribed.

Further examples of suitable paint additives are in the textbook "Paint Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998 , described.

The coating compositions according to the invention can be both solvent-based and aqueous. Solvent-based in this context means that the volatile constituents of the coating composition substantially, ie at least 51 wt .-%, preferably at least 60 wt .-%, based on the total volatile components, organic solvents (if present, including reactive diluents). Water-based in this context means that the volatile constituents of the coating composition substantially, ie at least 51 wt .-%, preferably at least 60 wt .-%, in particular at least 80 wt .-%, based on the total volatile components, water , Coating agents consist principally of volatile and nonvolatile constituents. The determination of the non-volatile content of the coating composition can after DIN EN ISO 3251 with the following test conditions: initial weight of (1 ± 0,1) g, then 24 hours of drying at 23 ° C, then (corresponding to DIN EN ISO 3251 appendix B1 ) 1 hour at 105 ° C. The volatile component is the difference between the total mass and the non-volatile component.

in the Difference to solvent-based coating agents have the aqueous coating agent as a solvent essentially water and no or only small amounts of organic Solvents. In the aqueous Beschich processing agents is the proportion of organic solvents preferably at most 30 wt .-%, particularly preferably at most 20 wt .-% and in particular at most 10 wt .-%, based on the total weight of those contained in the coating agent volatile components. A special version the coating compositions of the invention are water-based compositions containing only water as a solvent.

Suitable solvents for solvent-based coating agents are aliphatic, alicyclic, heterocyclic, aromatic and heteroaromatic hydrocarbons, esters of aliphatic carboxylic acids with C ₂ -C ₁₀ -alkanols or polyalkylene glycols, ketones, lactones, lactams, ethers, monohydric or polyhydric alcohols and mixtures thereof. The solvents are then preferably selected from toluene, xylenes, solvent naphtha, white spirit, ligroin, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methoxyethyl acetate, methoxypropyl acetate, ethoxyethyl acetate, ethoxypropyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, dipropylene glycol, dibutyl glycol, Methanol, ethanol, n-propanol, isopropanol, butanol and mixtures thereof.

The coating compositions may be in the form of aqueous coating compositions containing at least one inventive water-dilutable polyester resin A). These polyester resins, as stated above, preferably an acid number (determined after DIN 53402 . ISO 2114 ) in the range of 31 to 80 mg KOH / g, more preferably from 35 to 70 mg KOH / g, especially from 40 to 65 mg KOH / g. Polyester resins A) whose carboxyl groups are at least partially neutralized with a base are particularly suitable for this purpose. Suitable bases are, for. As alkali and alkaline earth metal hydroxides, alkali and alkaline earth metal carbonates, alkali and alkaline earth metal hydrogencarbonates, ammonia, amines, amino alcohols and mixtures thereof. These include NaOH, KOH, NH ₃ , primary, secondary and tertiary amines, such as triethylamine, and amino alcohols, such as triethanolamine, methyldiethanolamine or dimethylethanolamine. Preferably, at least one volatile amine is used. For the purposes of the invention, this is understood as meaning an amine which has a boiling point of not more than 100 ° C. under normal conditions (20 ° C., 1013 mbar).

The aqueous coating compositions according to the invention may be in addition to at least one polyester resin A) at least one binder component B).

In a special version contains the watery Coating agent as component B) at least one additional polymeric binder, which is in the form of an aqueous polymer dispersion is present. In the case of the polymers of the aqueous polymer dispersion they are primary dispersions, d. H. Polymer dispersions, by free radical aqueous emulsion polymerization and secondary dispersions, d. H. Polymer dispersions in which the dispersed polymer first by polymerization in an organic solvent and then the organic solvent was replaced by water. The additional polymeric binders can be used as physically drying dispersions, self-crosslinking Dispersions, UV-curable dispersions, thermosetting Dispersions, dispersible by the addition of a crosslinker dispersions (2-component dispersions) or dual-cure systems are present.

A first embodiment is aqueous coating compositions which contain a polyester resin according to the invention and additionally at least one physically drying polymer dispersion as binder. Such dispersions are well known to those skilled in the art, for. B. off D. Distler, "Aqueous Polymer Dispersions", Wiley-VCH Weinheim 1999, Chapter 6.5, from M. Schwartz, R. Baumstark, Water-based Acrylates for Decorative Coatings "Curt R. Vincentz-Verlag Hannover 2001, pp. 191-212 and literature cited therein as well as EP-A 184091 . EP-A 376096 . EP-A 379892 . EP-A 522789 . EP-A 609793 . EP-A 439207 . EP-A 609756 . EP-A 623659 . EP 710680 . WO 95/16720 . DE 12 20 613 . DE-A 34 18 524 . US 3,454,516 . US 5,263,193 . US 5,185,387 and US 5,021,469 , The physically drying dispersions are preferably aqueous polymer dispersions obtainable by emulsion polymerization of ethylenically unsaturated monomers, which are typically at least 80% by weight, eg. B. 80 to 100 wt .-% and especially 90 to 99 wt .-%, based on the total amount of monomers, at least one monoethylenically unsaturated monomer having a limited water solubility of usually ≤ 30 g / l at 25 ° C copolymerized (monomer M1). Examples of monomers (M1) are vinylaromatics such as styrene, vinyl esters of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate and the like, esters of monoethylenically unsaturated C ₃ -C ₆ -mono- and C ₄ -C ₆ -dicarboxylic acids with C ₁ -C ₁₀ -alkanols, in particular the esters of acrylic acid and methacrylic acid with C ₁ -C ₁₀ -alkanols such as ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate , n-hexyl methacrylate, 2-ethylhexyl methacrylate, furthermore butadiene and C ₂ -C ₆ olefins such as ethylene or propene. In addition, the monomers constituting the polymer of the aqueous polymer dispersion can be up to 20 wt .-%, z. B. 0.1 to 20 wt .-% and in particular 1 to 10 wt .-% of the monomers M1 different monomers (monomers M2) in copolymerized form. These include monoethylenically unsaturated acids having generally 2 to 10 carbon atoms, eg. B. mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, sulfonic acids such as vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and the same, amides of the aforementioned monoethylenically unsaturated carboxylic acids, eg. As acrylamide, methacrylamide, hydroxy-C ₂ -C ₄ alkyl esters of the aforementioned monoethylenically unsaturated monocarboxylic acids, eg. 2-hydroxyethyl acrylate, 2- and 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2- and 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate and monoethylenically unsaturated monomers having oligoalkylene oxide chains, preferably with polyethylene oxide chains having degrees of oligomerization, preferably in the range from 2 to 200, z. As monovinyl and monoallyl ethers of Oligoethylenglykolen and esters of acrylic acid, maleic acid or methacrylic acid with oligoethylene glycols. Suitable monomers M2 are also monoethylenically unsaturated, urea group-carrying monomers such as N-vinyl and N-allylurea and derivatives of imidazolidin-2-one, z. N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethyl-imidazolidin-2-one, N-allyloxyethyl-imidazolidin-2-one, N- (2-acrylamido-ethyl) imidazolidin-2-one, N- (2-acryloxyethyl ) imidazolidin-2-one, N- (2-methacrylamidoethyl) imidazolidin-2-one, N- (2-methacryloxyethyl) imidazolidin-2-one (= ureidomethacrylate), N- [2- (acryloxyacetamido) ethyl] imidazolidine-2 -on, N- [2- (2-acryloxyacetamido) ethyl] imidazolidin-2-one and N- [2- (2-methacryloxyacetamido) ethyl] imidazolidin-2-one.

Furthermore, the physically drying polymer dispersions (as well as the optionally mentioned self-crosslinking, actinic radiation-curing or thermosetting polymer dispersions) generally contain at least one surface-active sub punch for stabilizing the polymer dispersion. Suitable surface-active substances are the protective colloids and emulsifiers customarily used for carrying out free-radical aqueous emulsion polymerizations.

Suitable protective colloids are, for example, polyvinyl alcohols, starch and cellulose derivatives or vinylpyrrolidone-containing copolymers. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart 1961, pp. 411-420 ,

Preferred surface-active substances are emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 2000. They may be both anionic, cationic and nonionic in nature, with anionic emulsifiers and their combination with nonionic emulsifiers being preferred. The anionic emulsifiers include alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ -C ₁₂ ), of sulfuric monoesters of ethoxylated alkanols (EO degree: 2 to 50, alkyl radical: C ₁₂ -C ₁₈ ) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ -C ₉ ), of alkylsulfonic acids (alkyl radical: C ₁₂ -C ₁₈ ), of alkylarylsulfonic acids (alkyl radical: C ₉ -C ₁₈ ), and of mono- and dialkyldiphenyl ether sulfonates, as described, for example, in US Pat. In US 4,269,749 are described. Suitable nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ -C ₉ ), ethoxylates of long-chain alcohols (EO degree: 3 to 50, alkyl radical : C ₈ -C ₃₆ ), as well as polyethylene oxide / polypropylene oxide block copolymers. Preferred are ethoxylates of long-chain alkanols (alkyl radical: C ₁₀ -C ₂₂ , average degree of ethoxylation: 3 to 50) and particularly preferred those based on oxoalcohols and native alcohols with a linear or branched C ₁₂ -C ₁₈ -alkyl radical and a degree of ethoxylation of 8 until 50.

Provided the aqueous coating compositions according to the invention contain at least one surfactant is their content usually 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the total weight of the coating agent.

A second embodiment are aqueous coating compositions, a polyester resin according to the invention A) and additionally at least one aqueous dispersion self-crosslinking curable by actinic radiation or thermally curable binder polymer B).

in the Trap of self-crosslinking or crosslinkable polymer dispersions it is known to be aqueous polymer dispersions, whose polymers have reactive groups which together or with a crosslinking agent contained therein under bond formation react. Complementary to the above remarks reactive groups of the polymers and / or crosslinking agents are referred to taken.

at The polymers of self-crosslinking dispersions may be polymers based on ethylenically unsaturated monomers, as before described for the physically drying dispersions, act, contain the corresponding functional monomers in copolymerized form. Also suitable are polyurethane-based dispersions by Incorporation of appropriate monomers and / or by choice of stoichiometry the polyurethane forming monomers the desired have functional groups.

in the Case of thermosetting polymer dispersions is to customary aqueous dispersions of thermally curable polymers or prepolymers. In particular, such polymer dispersions comprise at least one Polymer component based on a polyurethane or based on a Emulsion polymer of ethylenically unsaturated monomers, wherein the polymer component hydroxyl groups, Ke togruppen, urea groups, Having epoxide groups and / or carboxyl groups, and at least a low molecular weight or polymeric crosslinker with at least two reactive groups as mentioned above.

Surprisingly show the polyester resins A) according to the invention based on 2-Propylheptansäureglycidester and / or 4-methyl-2-propylhexansäureglycidester compared to an improved hydrolytic stability Polyester resins known from the prior art. They are suitable thus particularly advantageous for use in aqueous Coating agents.

The Polyester resins A) according to the invention are suitable furthermore as soft resins, d. H. as softening (plasticizing) Component in combination with one or more synthetic hard resins. Another object of the invention is therefore the use of a Polyester resin, as defined above, as a plasticizing component a physically drying coating agent, in addition contains at least one hard resin. The latter are preferred selected from cellulose nitrate resins, PVC homopolymers and copolymers, Acrylate resins, ketone resins and mixtures thereof.

Another object of the invention is a coating composition comprising at least one polyester resin based on 2-Propylheptansäureglycides ter and / or 4-methyl-2-propylhexansäureglycidester, as defined above and contains at least one cellulose nitrate.

cellulose nitrates are paint-type binders and are also called nitrocellulose paints referred to, which are so-called nitro paints or nitro combination paints can act. This is generally understood to be solvent-based, physical drying coating compositions which act as a binder cellulose nitrate, optionally in combination with one or more thereof paint typical binders, included. If necessary, you can the coating compositions of the invention, the at least one polyester resin and at least one cellulose nitrate additionally containing at least one of the polyesters contain various plasticizers. Typical plasticizers include Dialkyl adipates, dialkyl phthalates, tricresyl phosphates, etc. By the use according to the invention of the polyester resins based on 2-Propylheptansäureglycidestern and / or 4-methyl-2-propylhexanoic acid glycidyl esters may be used additional plasticizer partially or completely be waived. The coating compositions of the invention, the at least one polyester resin and at least one cellulose nitrate are preferably solvent-based coating compositions. On the aforementioned organic solvent is Referenced.

The Polyester resins according to the invention are also suitable advantageous in combination with paint typical polyisocyanates as Binders in two-component polyurethane coatings. Another item The invention is therefore a coating composition which at least a polyester resin as defined above, and at least one polyisocyanate contains.

coating agents Polyisocyanate based in addition to the polyester resins according to the invention at least one further, different polyhydroxyl compound included. This is preferably selected from polyester polyols, polyether polyols, Polyacrylate polyols and mixtures thereof. Preferred is the proportion of polyester resins according to the invention at least 10% by weight, more preferably at least 50% by weight, in particular at least 80% by weight, based on the total weight the polyhydroxyl compounds contained in the coating agent. In a special embodiment contains the coating agent only polyester resins according to the invention as polyhydroxyl compounds.

suitable Polyisocyanates are those known to those skilled in the preparation of polyurethane coatings Links. The molar ratio of isocyanate groups to Hydroxyl groups is preferably 2: 1 to 1: 2, especially preferably 1.5: 1 to 1: 1.5. Any excess Isocyanate groups may, for. B. with water (for example in the form of atmospheric moisture) and thus to harden contribute.

When Polyisocyanates are known from the prior art aliphatic, cycloaliphatic or aromatic isocyanates in question. These can be two or more (e.g., 3, 4, 5, 6) isocyanate groups per molecule exhibit. Preferred polyisocyanates are tetramethylene diisocyanate, Hexamethylene diisocyanate (HDI), 1,4-diisocyanato-4-methylpentane, 2-butyl-2-ethylpentamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 4-isocyanatomethyl-1,8-octamethylene diisocyanate, Dodecyl diisocyanate, isophorone diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 1,4-diisocyanatocyclohexane, 2,4'-methylenebis (cyclohexyl) diisocyanate, 4,4'-methylenebis (cyclohexyl) diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), tolidine diisocyanate, Triisocyanatotoluene, 3 (4) isocyanatomethyl-1-methylcyclohexyl isocyanate, 4-methylcyclohexane-1,3-diisocyanate (H-TDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), xylylene diisocyanate, tetramethylxylylene diisocyanate and Mixtures thereof.

Farther For example, oligo- or polyisocyanates can be used are made of said di- or polyisocyanates or their mixtures by linking by means of urethane, allophanate, Urea, biuret, uretdione, amide, isocyanurate, carbodiimide, Uretonimine, oxadiazinetrione or iminooxadiazinedione structures let produce. These include z. Biuret, allophanate or isocyanurate-containing polyisocyanates based on aliphatic Diisocyanates, such as HDI. Also suitable are so-called capped Diisocyanates with reversibly blocked NCO groups.

The coating compositions according to the invention, at least a polyester resin and at least one polyisocyanate are preferably solvent-based coating compositions. On the aforementioned organic solvent is Referenced. The solvent content can be up to 80 Wt .-%, preferably up to 60 wt .-%, in particular up to 45 wt .-%, based on the total weight of the coating agent. In an alternative embodiment, the combination is used of at least one polyester resin and at least one polyisocyanate for the preparation of an aqueous polyurethane dispersion.

The coating compositions of the invention usually have a solids content of 20 to 85 wt .-%, preferably 40 to 80 wt .-%, be absorbed the total weight of the coating agent.

• – 10 bis 70 Gew.-%, Polyesterharz A), erhältlich durch Polykondensation eines Gemischs, enthaltend 2-Propylheptansäureglycidester und/oder 4-Methyl-2-propylhexansäureglycidester, wie zuvor definiert,
• – 0 bis 70 Gew.-% Pigmente, Solvent-Farbstoffe und/oder Füllstoffe C),
• – 0 bis 30 Gew.-% übliche Zusatzstoffe C), und
• – Wasser und/oder organisches Lösungsmittel auf 100 Gew.-%.

A typical coating agent contains:

• 10 to 70% by weight, polyester resin A), obtainable by polycondensation of a mixture containing 2-propylheptanoic acid glycidyl ester and / or 4-methyl-2-propylhexanoic acid glycidyl ester, as defined above,
• 0 to 70% by weight of pigments, solvent dyes and / or fillers C),
• - 0 to 30 wt .-% of conventional additives C), and
• - Water and / or organic solvent to 100 wt .-%.

The Preparation of the paints according to the invention takes place in a known manner by mixing the components in this customary Mixing devices.

The Application of the surface treatment agent takes place in in a known manner, for. B. by brushing, spraying, dipping, Rollers, doctor blades, electrostatic methods, etc., whereby the Application method in a conventional manner according to the type of Coating agent, the nature and shape of the objects to be coated and the technical conditions.

The coating compositions of the invention are suitable in principle for a large variety of metallic and non-metallic substrates. These include substrates made of metal, wood, plastic, glass, etc. The invention Coating agents are especially suitable for use in the painting of automobiles. They are still suitable as Architectural paints, d. H. for coating buildings or Buildings. It may be mineral substrates such as plasters, plaster or plasterboard, masonry or concrete to Wood, wood materials, metal or paper, z. B. wallpaper or plastic, z. As PVC, polyester-reinforced fabrics, polyurethanes, etc., act.

The consisting of the polyester of the invention Coating may be used as a primer, filler, pigmented Topcoat or basecoat, or as clearcoat be used. It can be used as the sole coating agent or used in one or more layers of a multilayer coating become. It is also especially suitable for coating pretreated Substrates, such as metals with conventional primers, etc. The application of the coating agent may in one step or in several Steps take place, for. B. in 1, 2 or 3 steps. Furthermore, can you also successively two or more coating agents, for. B. one or more primers or primers in combination with apply one or more topcoats, so that you have a multi-layered, z. B. a 2-, 3-, 4- or 5-layer coating structure receives. Between the individual application steps, drying and / or curing steps are performed. Depending on the type of coating agent and the desired Coating can also make the coating agents wet-on-wet be applied.

The amount of surface treatment agent applied depends in a manner known per se on the desired properties of the treated surface and is typically in the range of 1 to 500 g / m ² , calculated as non-volatile constituents of the coating composition. In a multi-layered construction, the amount of coating agent is typically 1 to 200 g / m ² per layer.

In The rule involves applying the surface treatment agent also a drying step. Here are the possibly existing volatiles of the surface treatment agent removed and / or curing of the surface treatment agent contained curable ingredients. Accordingly, the drying conditions are addressed in themselves known manner on the type of surface treatment agent. In the case of physically drying coating agent is the Drying temperature typically in the range of 20 to 80 ° C. and the drying time is in the range of 10 minutes to 24 hours. in the Traps of thermally crosslinkable systems depend on drying time and temperature in a conventional manner of the reactivity functional groups and the type of system chosen in principle, temperatures ranging from 20 ° C to 220 ° C are suitable. The curing of UV-curing systems is done by using actinic radiation such as UV light or Electron beams. In dual-cure systems, one usually gets first a UV cure and then perform a thermal cure.

The Invention will be apparent from the following non-limiting Examples explained in more detail.

Examples

The determination of the non-volatile content of the coating composition can after DIN EN ISO 3251 with the following test conditions: initial weight of (1 ± 0,1) g, then 24 hours of drying at 23 ° C, then (corresponding to DIN EN ISO 3251 appendix B1 ) for one hour at 105 ° C.

The determination of the gloss of the coating composition can after ISO 2813 ( DIN 67530 ) respectively. The specimen is placed in a calibrated reflectometer, and at a defined angle of incidence (here 20 ° and 60 °), it is determined to what extent that reflected light has been reflected or scattered. The determined reflectometer value is a measure of the gloss (the higher the value, the higher the gloss).

The Penetration hardness of the coating agent is determined by the Fisherscope method certainly.

Example 1.1

In a laboratory reactor with adjustable, electrical resistance heating; Product temperature control; Nitrogen inlet; Randgängigem, steplessly adjustable stirrer; ascending water and reflux condenser and descending distillation bridge with xylene-filled water are weighed 156.9 g of trimethylolpropane, 429.8 g of glycidyl ester of 2-propylheptanoic, 412.0 g of phthalic anhydride, 10.9 g of maleic anhydride and 30 g of xylene as entraining agent. It is slowly heated to 140 ° C and held at this temperature for 30 minutes. Then the temperature is continuously increased over four hours to max. Increased 210 ° C, so that the entrainer is distilled quickly and a total of 15.3 g of reaction water is deposited. Starting at 190 ° C, the acid number ( ISO 2114 ) and the melt viscosity in a plate-and-cone viscometer at 150 ° C. ( ISO 291 ). The temperature is maintained at 210 ° C until an acid number of 10 mg KOH / g is reached. Then, entrainer and residual water are distilled off via the descending distillation bridge. It is then cooled to a temperature below 160 ° C and the reaction product with 100.0 g of solvent, consisting of an aromatic fraction having the boiling limits 158 to 172 ° C, dissolved. The solution is discharged and diluted with 290.0 g of the same solvent. Finally, the resulting solution with 38.0 g of the same solvent on a solid (nfA = non-volatile content, measured after 30 minutes at 130 ° C in a convection oven, otherwise after ISO 3251 ) of 70%. The product has a viscosity of 65 dPas, measured in a plate-and-cone viscometer ( ISO 3219 ) at 23 ° C, an iodine color number ( DIN 6162 ) of 15; an acid number of 6 mg KOH / g and an OH number ( DIN 53240 ) of 97 mg KOH / g, both based on the solids (nfA).

Comparative Example 1.2

The procedure is as in Example 1.1, but instead of the glycidyl ester of 2-propylheptanoic the glycidyl ester of neodecanoic acid (Cardura ^® E 10 P from Hexion) is weighed. The resulting product has a viscosity of 75 dPas, measured in a plate-and-cone viscometer at a solids content of 70.0% ( ISO 291 ) at 23 ° C, an iodine color number ( DIN 6162 ) of 27; an acid number of 7 mg KOH / g and an OH number ( DIN 53240 ) of 95 mg KOH / g, both based on the solids (nfA).

Example 1.3 Paint Testing

From the products of Examples 1.1 and 1.2 simple paints are prepared, each consisting of 75.0% of the alkyd resin solutions prepared (70% in said aromatic solvent), 17.5% of a Hexamethoxymethylmelaminharzes (Luwipal ^® 066 BASF), 4.5% n-Butanol, 0.6% of a 10% solution of the polyether-modified silicone oil Baysilon ^® OL 44 (Borchers) in n-butanol and 2.40% of a 25% solution of p-toluenesulfonic acid in n-butanol and a processing solids of Have 70%. The paint with the binder according to the invention of Example 1.1 has a viscosity which is only 75% of the viscosity of the paint based on the binder of Comparative Example 1.2.

The paints are applied by means of a doctor blade to a black primed steel sheet, flashed for 5 minutes and then baked at 140 ° C for 20 minutes. The examination of the lacquers after a few hours of aging gave (results of the comparative example in parentheses) at a layer thickness of 30 μm the following results:
Shine ( ISO 2813 ) at 60 ° geometry: 98.2% (97.2%)
Gloss at 20 ° Geometry: 94.6% (92.5%)
Penetration Hardness: 132 (145)

The Chemical resistance is by a 30-minute Exposure of a 10% sulfuric acid to the film surface tested and showed for both paint systems up to and including 40 ° C no impairment and for both Lacke only a slight impairment at 50 ° C.

Next the gloss shows the paint with the invention Binders a better flow and better flexibility.

Example 2.1:

The procedure is as in Example 1.1. Weighed are 228.2 g of trimethylolpropane, 356.0 g of glycidyl ester of propylheptanoic acid, 437.2 g of hexahydrophthalic anhydride and 30 g of xylene as an entraining agent. The dissolution, dilution and adjustment of the solid are carried out with the same amounts of solvent as in Example 1.1. The resulting product has a viscosity of 21.3 dPas, measured in a plate-and-cone viscometer at a solids content of 70.0% ( ISO 291 ) at 23 ° C, an iodine color number ( DIN 6162 ) of 10; an acid number of 5 mg KOH / g and an OH number ( DIN 53240 ) of 147 mg KOH / g, both based on the solids (nfA).

Comparative Example 2.2:

The procedure is as in Example 2.1, but instead of the glycidyl ester of 2-propylheptanoic is the glycidyl ester of neodecanoic acid (Cardura ^® E 10 P of the hexion). The resulting product has a viscosity of 33.7 dPas, measured in a plate-and-cone viscometer at a solids content of 70.0% ( ISO 3219 ) at 23 ° C, an iodine color number ( DIN 6162 ) of 22; an acid number of 6 mg KOH / g and an OH number ( DIN 53240 ) of 145 mg KOH / g, both based on the solids (nfA).

Example 2.3 Paint Testing

Two-component clearcoats are each made of the products of Examples 2.1 and 2.2, consisting of 70% stock paint, containing 62.7% of the alkyd resin described in Examples 2.1 and 2.2, 0.7% of a Radikalquenchers (Tinuvin ^® 292 from Ciba) 0.7% of a UV absorber (Tinuvin 1130 of Ciba ^®), 1.0% of a 10% solution of a polyether-modified silicone oil (Baysilon ^® OL 17 from Borchers) and 1.0% of a 5% solution of dibutyltin dilaurate as Crosslinking catalyst, 3.9% n-butyl acetate; and 30% hardener of 23.5% of an isocyanurate trimer of hexamethylene diisocyanate (Basonat HI ^® 90%) and 6.50% n-butyl acetate exist. Base lacquer and hardener are only mixed immediately before application.

The Mixture has a processing solids of 70%, with the paint with the binder according to the invention of Example 2.1 has a viscosity that is only 65% of the Viscosity of the paint based on the binder of the comparative example 2.2 has.

The paints are applied by means of a doctor blade to a black primed steel sheet, flashed for 5 minutes and then baked at 80 ° C for 20 minutes. Examination of the paints after a few hours of aging gave (results of the comparative example in parentheses) at a layer thickness of 30 μm the following results:
Shine ( ISO 2813 ) at 60 ° geometry: 83.0% (83.3%)
Penetration Hardness: 98 (121)

The Chemical resistance was through a 30-minute Exposure of a 10% sulfuric acid to the film surface tested and showed for both paint systems up to and including 40 ° C no impairment and for both Lacke only a slight impairment at 50 ° C.

To a longer storage time will be induration reached from 140 (145). The paint with the invention Binder shows better flow and better flexibility.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• US 6277497 [0006]
• EP 1754737 A1 [0007]
• - EP 07111275 [0008]
• - DE 10239134 A [0021]
• - DE 2107084 A [0028]
• - DE 2446944 A [0029]
• EP 0697018A [0030]
• - US 5036154 [0031]
• EP 1115714 [0032]
• WO 00/44836 [0033]
• - DE 3636183 A [0075]
• WO 94/22968 [0090]
• EP 0276501 A [0090]
• EP 0249201 A [0090]
• WO 97/12945 [0090]
• - EP 0008127 A [0090]
• EP 184091A [0098]
• - EP 376096 A [0098]
• - EP 379892 A [0098]
• - EP 522789 A [0098]
• - EP 609793 A [0098]
• - EP 439207A [0098]
• - EP 609756A [0098]
• - EP 623659 A [0098]
• - EP 710680 [0098]
• WO 95/16720 [0098]
• - DE 1220613 [0098]
• - DE 3418524 A [0098]
• - US 3454516 [0098]
• - US 5263193 [0098]
• US 5185387 [0098]
• US 5021469 [0098]
• US 4269749 [0101]

Cited non-patent literature

• - Rompp-Lexicon "Paints and printing inks", Georg-Thieme-Verlag, Stuttgart, 1998, p 20-22 [0003]
• H. Wagner and HF Sarx in Lackkunstharze, 5th edition, Carl Hanser Verlag, Munich (1971), pp. 96-99 [0005]
• - Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie Weinheim, 4th edition (1980), Volume 19, pages 61 et seq. [0043]
• H. Wagner and HF Sarx, "Lackkunstharze", Carl Hanser Verlag, Munich (1971), pages 86-152 [0043]
• - ISO 291 [0053]
• - DIN 6162 [0055]
• - DIN 53240 [0056]
• - DIN 53240 [0056]
• - DIN 53402 [0057]
• - ISO 2114 [0057]
• - DIN 53402 [0057]
• - ISO 2114 [0057]
• - DIN 53402 [0057]
• - ISO 2114 [0057]
• - PKT Oldring (Editor), Chemistry and Technology of UV and EB Formulations for Coatings and Paints, Vol. II, SITA Technology, London, 1991, pp. 37-206 [0064]
• JP Fouassier (ed.), Radiation Curing in Polymer Science and Technology, Elsevier Science Publisher Ltd., 1993, Vol. 1, pp. 237-240 [0070]
• - Römpp-Lexikon, Paints and Printing Inks , Georg Thieme Verlag, 1998, page 176 [0075]
• - Römpp-Lexikon, Paints and Printing Inks , Georg Thieme Verlag, 1998, pages 250 ff. [0078]
• Römpp-Lexikon, Paints and Printing Inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Thickening Agents", p. 599-600 [0090]
• - "Paint Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pp. 51-59 and 65 [0090]
• - "Paint Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998 [0091]
• - DIN EN ISO 3251 [0092]
• - DIN EN ISO 3251 Annex B1 [0092]
• - DIN 53402 [0095]
• - ISO 2114 [0095]
• D. Distler, "Aqueous Polymer Dispersions", Wiley-VCH Weinheim 1999, Chapter 6.5, from M. Schwartz, R. Baumstark, Water-based Acrylates for Decorative Coatings "Curt R. Vincentz-Verlag Hannover 2001, pp. 191-212 [0098 ]
• - Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart 1961, pp. 411-420 [0100]
• - DIN EN ISO 3251 [0126]
• - DIN EN ISO 3251 Annex B1 [0126]
• - ISO 2813 [0127]
• - DIN 67530 [0127]
• - ISO 2114 [0129]
• - ISO 291 [0129]
• - ISO 3251 [0129]
• - ISO 3219 [0129]
• - DIN 6162 [0129]
• - DIN 53240 [0129]
• - ISO 291 [0130]
• - DIN 6162 [0130]
• - DIN 53240 [0130]
• - ISO 2813 [0132]
• - ISO 291 [0135]
• - DIN 6162 [0135]
• - DIN 53240 [0135]
• - ISO 3219 [0136]
• - DIN 6162 [0136]
• - DIN 53240 [0136]
• - ISO 2813 [0139]

Claims (15)

Polyester resin A), obtainable by polycondensation a mixture containing a) at least one polyol, b) at least one polycarboxylic acid or a derivative thereof, c) 2-Propylheptansäureglycidester and / or 4-methyl-2-propylhexansäureglycidester. Polyester resin according to claim 1, wherein the polycondensation used mixture additionally as component d) at least a hydroxycarboxylic acid or a derivative thereof. Polyester resin according to one of the preceding claims, wherein the mixture used for the polycondensation additionally as component e) at least one monocarboxylic acid or contains a derivative thereof which is derived from component c) is different. Polyester resin according to one of the preceding claims, wherein the mixture used for the polycondensation, based on the total weight of the mixture, 5 to 75% by weight, preferably 10 to 50% by weight containing component c). Coating composition containing at least one polyester resin A) as defined in any one of claims 1 to 4. Coating composition according to claim 5 in physical drying, self-crosslinking or displaceable form. Coating composition according to one of the claims 5 or 6, which additionally comprises at least one binder component B), preferably selected from among the polyester resins A) various polymeric binders, crosslinking agents, of crosslinking agents different reactive diluents and mixtures thereof. Coating composition according to one of the claims 5 to 7, which additionally contains at least one of the polyester resins A) contains various polymeric binder B), the is selected from physically drying binders, self-crosslinking binders, binders curable with actinic radiation, thermally curable binders, by adding a crosslinker crosslinkable binders, dual-cure binders, and combinations thereof. Coating composition according to one of the claims 5 to 8, the at least one polyester resin A) and at least one Binder component B), selected is aminoplast, melamine resins, urea resins, acrylate or copolymers, amide resins, polyepoxides, epoxy resins, siloxanes, Silicone resins, polyisocyanates, polyurethanes, polyureas, Polyester acrylates, polylactones, polycarbonates, polyethers, phenolic resins, optionally partially saponified polyvinyl esters, oils, natural resins and mixtures thereof. Coating composition according to one of the claims 5-9 containing an additive C) selected is among pigments, dyes, nanoparticles, fillers, Flow control agents, plasticisers, biocides, defoamers, Antioxidants, UV stabilizers, slip additives, emulsifiers, protective colloids, Wetting agents, deaerators, film-forming aids, Adhesion promoters, crosslinking catalysts, photoinitiators, radical-forming Initiators, polymerization inhibitors, corrosion inhibitors, rheology-modifying Additives, antifreeze, flame retardants and mixtures from that. Aqueous coating agent that at least a water-dilutable polyester resin A) as in any of Claims 1 to 4 defined, having an acid number in the range of 31 to 80 mg KOH / g. Use of a polyester resin A), as in one of claims 1 to 4, as a plasticizing component a physically drying coating agent. Use according to claim 12, wherein the coating agent additionally contains at least one binder component B), which is selected from cellulose nitrates, PVC homo- and Copolymers, acrylate resins, ketone resins and mixtures thereof. Coating composition containing at least one polyester resin A) as defined in any one of claims 1 to 4, and at least a cellulose nitrate. Coating composition containing at least one polyester resin A) as defined in any one of claims 1 to 4, and at least a polyisocyanate.