WO1996013558A1

WO1996013558A1 - Unsaturated binder composition

Info

Publication number: WO1996013558A1
Application number: PCT/SE1995/001218
Authority: WO
Inventors: Kent SÖRENSEN; Bo Pettersson
Original assignee: Perstorp Ab
Priority date: 1994-10-27
Filing date: 1995-10-18
Publication date: 1996-05-09
Also published as: AU3861195A; SE9403680L; SE502634C2; SE9403680D0

Abstract

Unsaturated binder composition comprising at least one unsaturated monomer, at least one unsaturated polyester and preferably one or more crosslinking catalysts or the like. The monomer is preferably an ester of at least one carboxylic acid or anhydride and at least one alcohol or an adduct thereof and includes in its molecule at least one reactive aliphatic unsaturation, which can be corsslinked with the unsaturation within the polyester. The polyester is a dendritic or hyperbranched macromolecule comprising a nucleus having at least one reactive hydroxyl or epoxide group and anumber of generations of at least one chain extender having at least two hydroxyl groups and at least one carboxyl group. The macromolecule is completely or partially in one or more steps chain terminated by at least one chain terminator being a carboxyfunctional unsaturated ester, a saturated or unsaturated carboxylic acid or by allylation.

Description

UNSATURATED BINDER COMPOSITION

The present invention relates to a binder composition comprising at least one unsaturated monomer, at least one unsaturated polyester and preferably one or more crossiinking catalysts and/or crossiinking initiators and/or similar additives. The polyester is a chain terminated hyperbranched or dendritic macromolecule and unsaturation within the monomer can be crosslinked with unsaturation within the polyester.

Unsaturated polyesters are curing and/or drying high molecular compounds used for i.a. composites, paints, lacquers and similar binders and can roughly be divided into conventional polyesters and dendritic or hyperbranched macromolecules of polyester type.

Conventional unsaturated polyesters are mainly based on unsaturated and saturated carboxylic acids, such as maleic acid, fumaric acid, o-phthalic acid, tetrahydrophthalic acid, isophthalic acid, adipic acid, which are esterified with alcohols, preferably aliphatic saturated diols, such as ethylene glycol, propylene glycol, neopentyl glycol. Unsaturated alcohols, for example allyl ethers of trimethylolpropane or pentaerythritol, can also be included as well as minor amounts of polyfunctional alcohols.

Dendritic and hyperbranched macromolecules of polyester type are three dimensional molecules having a tree-like structure and are composed of a nucleus or initiator molecule having one or more reactive groups, preferable amine, hydroxyl or epoxide groups, to which one or more generations of a chain extender, such as saturated or unsaturated hydroxyfunctional carboxylic acids or reaction products thereof, are added. A macromolecule according to above can furthermore be chain terminated by for instance a saturated or unsaturated carboxylic acid or alcohol. Unsaturated polyesters having so high a molecular weight that good properties are obtained, but so low a viscosity that conventional solvents are unnecessary to add in order to obtain practical viscosities, can be prepared if the polyester is formulated as a dendritic or hyperbranched macromolecule

Crossiinking of unsaturated polyesters are performed by means of addition of various catalysts, such as peroxides and cobalt salts, or initiators for ultraviolet (UV) infrared (IR) or electron beam (EB) curing. A three dimensional structure is obtained through crossiinking of unsaturation within the polyester Even if direct crossiinking of the unsaturation within the polyester is possible, the obtained three dimensional crosslinked matrix often gives unfavourable properties, such as poor through cure, poor resistance etc. The crossiinking is usually aided by vinyl monomers, normally consisting of only styrene or wherein styrene is the main component. The polyester is thereby dissolved in and mixed with the monomer and constitutes normally 40-80% of the thus obtained binder composition. Compounds such as styrene are, in addition to being monomers, viscosity reducing, whereby high molecular and hence high viscous conventional unsaturated polyesters obtain a practical viscosity.

A variety among unsaturated polyesters are various acrylic oligomers of polyester type, i.e. polyesters wherein the unsaturation is derived from acrylic or methacrylic acid. Crossiinking is in these systems usually performed by means of an acrylic monomers, i. e. esters of mono, di, tri or polyfunctional alcohols and acrylic or methacrylic acid.

The large amounts of mainly styrene, used for crossiinking of unsaturated polyesters, has for a long time been subject to discussions and trials to eliminate or minimise the use has during the last years become more and more immediate. Most vinyl monomers are more or less injurious to the environment and/or hazardous to the health. Styrene is an inflammable liquid, with pungent odour, which at inhalation or vapour contact gives rise to nasal and pharyngeal burn, tear flow, headache, fatigue, nausea, vertigo, inflamed eyelids and at higher amounts respiratory disorders and unconsciousness. Long-term and repeated exposure to styrene can decrease the reaction ability and the memory. Furthermore, styrene degreases the skin and can cause blush, skin crack, blistering and eczema Mutagenic effect of styrene (mainly metabolites) has been proven in genetic tests Chromosomal anomaly has in some cases been proven in exposed persons. It can also be mentioned that the hygienic limit for styrene is as low as 25 ppm

Another problem at the use of vinyl monomers is that these polymerise, however slowly, already at room temperature. The polymerisation is rapid under influence of light, air, heat, alkali metals and peroxides. Styrene for instance polymerises very rapidly under a heavy exotherm at temperatures above 50°C This tendency to polymerisation reduces substantially the storage stability of unsaturated polyesters dissolved in and mixed with for instance styrene in comparison to the storage stability of the polyester per se. Vinyl polymers are, in order not to polymerise during employment, normally stabilised using various inhibitors, which per se can cause environmental and heath hazards and/or interact with the crossiinking mechanism of unsaturated polyesters. The trials made to reduce or eliminate the use of mainly styrene have substantially meant that various types of conventional branched and linear polyester has been formulated especially to be possible to crosslink with acceptable result without monomers. These trials have most often resulted in compromises with regard to the various properties, such as the relations between curing time, through cure, hardness, flexibility, resistance, molecular weight, viscosity etc. Non-reactive solvents, such as acetates, alcohols etc. , have often been added to obtain practical viscosities. These additions of solvents are from many aspects unsuitable. They give for instance rise to undesirable environmental, health and pratical problems. Coating and curing equipment is for instance not suitable or intended to be exposed to volatile solvents. In order to avoid contact between solvent vapours and high energy equipment, such as UV lamps and the like, the solvent in which the polyester is dissolved must be allowed to vaporise prior to curing, which depending on type of solvent, type of polyester and type of application can be a substantial bottle-neck in a production chain.

It has through the present invention quite unexpectedly been possible to eliminate above disclosed problems and produce an unsaturated binder composition, being entirely free of vinyl monomers of the styrene type, having good to excellent properties. The binder composition can, furthermore, in most cases be used without any addition of diluting solvents. The present invention provides a binder composition without waiving such properties as coating quality, final hardness, through cure, residual unsaturation, flexibility, impact resistance, hydrolytic stability etc.

The binder composition according to the present invention comprises at least one unsaturated monomer, at least one unsaturated polyester and preferably one or more crossiinking catalysts, crossiinking initiators and/or similar additives The unsaturation within the monomer is crosslinked with the unsaturation within the polyester The binder composition is characterised in a) that the monomer is

(i) an ester of at least one di, tri or polyfunctional aliphatic, cycloaliphatic or aromatic carboxylic acid or, where applicable, corresponding anhydride and at least one monofunctional aliphatic, cycloaliphatic or aromatic alcohol, (ii) an ester of at least one linear aliphatic monofunctional carboxylic acid having more than 3 carbon atoms, a branched aliphatic monofunctional carboxylic acid having more than 4 carbon atoms, a cycloaliphatic or aromatic monofunctional carboxylic acid and at least one mono, di, tri or polyfunctional aliphatic, cycloaliphatic or aromatic alcohol, (iii) an ester of a linear aliphatic monofunctional carboxylic acid having more than 3 carbon atoms, a branched aliphatic monofunctional carboxylic acid having more than 4 carbon atoms, a cycloaliphatic or aromatic monofunctional carboxylic acid and a monofunctional aliphatic, cycloaliphatic or aromatic alcohol,

(iv) a carboxyfunctional allyl ether or an ester thereof,

(v) an adduct between at least one carboxyfunctional compound according to (i) or (iv) and at least one di, tri or polyfunctional aliphatic, cycloaliphatic or aromatic alcohol,

(vi) an adduct between at least one hydroxyfunctional compound according to (ii) or (iv) and at least one di, tri or polyfunctional aliphatic, cycloaliphatic or aromatic carboxylic acid or, where applicable, corresponding anhydride, whereby the unsaturation within the monomer is derived from a carboxylic acid, an anhydride, an allyl ether and/or an alcohol, and b) that the polyester is a dendritic or hyperbranched macromolecule comprising a nucleus having at least one reactive hydroxyl or epoxide group to which

1 - 100, preferably 1 -20, generations of at least one monomeric or polymeric chain extender having at least two reactive hydroxyl groups and at least one reactive carboxyl group, are added, whereby a hyperbranched or dendritic macromolecule wherein terminal groups substantially are hydroxyl groups is yielded, which macromolecule completelt or partially in one or more steps is chain terminated

(i) by at least one chain terminator being a carboxyfunctional unsaturated ester of at least one di, tri or polyfunctional carboxylic acid or, where applicable, corresponding anhydride and at least one monofunctional alcohol, and/or

(ii) by a complete or partial allylation of the terminal hydroxyl groups of the macromolecule and optionally

(iii) by at least one chain terminator being a monofunctional saturated or unsaturated carboxylic acid or, where applicable, corresponding anhydride, whereby the unsaturation within the polyester completely or partially is derived from the chain termination.

The, in the binder composition according to the present invention, included monomer is in various embodiments of the general formula

( R₁ - O - R₄)_n - R₂ - (R₄ - O - R₃)_m wherein n and m independently is 1 , 2 or 3 and wherein R_j is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, R₂ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, R₃ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof and

O H

II I wherein R. is C or C

I

H

whereby at least one substituent R, , R₂ or R₃ comprises at least one aliphatic double bond.

O

II

R₂ can, in the embodiment wherein R₄ is C, be carboxysubstituted alkyl, alkenyl alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof and R, can be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or hydroxysubstituted variations thereof.

R₃ can, furthermore, in this embodiment be O O

I! II

R₅ - O - C - R₆ - C - O - R₇ wherein R₅ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, R₆ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or hydroxysubstituted variations thereof and R₇ is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof

R₂ can, in the alternative embodiment wherein R₄ is CH₂, be hydroxysubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or carboxysubstituted variations thereof.

R₃ can, furthermore, in this embodiment be R₅ - O - CH₂ - R₆ - CH₂ - O - R₇ wherein R₅ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, R₆ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or carboxysubstituted variations thereof and R₇ is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof

The monomer is, in a preferred embodiment of the present invention, an ester of a mono or difunctional carboxylic acid or, where applicable, its anhydride and a monofunctional alcohol, the molar ratio between carboxylic acid and alcohol being 1 0 8 to 1 1.2 The carboxylic acid or the anhydride is preferably maleic anhydride, fumaric acid, succinic anhydride, adipic acid, propionic acid, acetic acid, crotonic acid, caprylic acid or capric acid while the alcohol preferably is trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 5-methyl- l ,3-dioxane-5-methanol, methanol, ethanol, propanol or butanol The monomer thereby comprises at least one aliphatic double bond

The monomer is in a further embodiment an adduct between

(a) an ester of maleic anhydride or fumaric acid and a monofunctional alcohol, such as methanol, ethanol, propanol, butanol or 1 ,3-dioxane or allyl ether monoalcohols and

(b) a diol, whereby the diol is ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 2-methyl- l ,3-propanediol, 2-ethyl-2-butyl- l ,3-propanediol, l ,3-dioxane-5,5-dimethanol, cyclohexanedimethanol, trimethylolpropane monoallyl ether and/or phenylethylene glycol

The molar ratio ester (a) to diol (b) is in these embodiments 0 8 1 to 2 2 1

The monomer is, in yet a further embodiment, an adduct between

(a) an ester of maleic anhydride or fumaric acid and an aliphatic monofunctional alcohol, such as methanol, ethanol, propanol or butanol,

(b) a diol and

(c) a monofunctional carboxylic acid

The diol in above embodiment is preferably ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 2-methyl- l ,3-propanediol, 2-ethyl-2-butyl- l ,3- propanediol, cyclohexanedimethanol, l ,3-dioxane-5,5-dimethanol, trimethylol¬ propane monoallyl ether or phenylethylene glycol while the carboxylic acid preferably is crotonic acid, caprylic acid or capric acid The molar ratio ester to diol to acid is 1 0 8 0 8 to 1 1 2 1 2

The monomer is in certain embodiments 2,2-dimethylolpropionic acid monoallyl ether or 2,2-dimethylolpropionic acid diallyl ether or an ester thereof and for instance trimethylolpropane diallyl ether or pentaerythritol triallyl ether at a molar ratio 1 0 8 to 1 1 2 The monomer can alternatively be an ester of 2,2-dimethylolpropionic acid monoallyl ether or 2,2-dimethylolpropionic acid diallyl ether and a diol at a molar ratio 0 8 1 to 2 2 1 , the diol being ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 2-methyl- l ,3-propanediol, 2-ethyl-2-butyl- l ,3 -propanediol, cyclohexane dimethanol, l ,3-dioxane-5,5-dimethanol, trimethylolpropane monoallyl ether or phenylethylene glycol

The choice of compounds included in the monomer, the degree of unsaturation, the location of the unsaturation within the molecule and the viscosity as well as the amount of monomer influence to a varying extent the properties of the binder composition according to the present invention Best properties are in most cases obtained if the binder composition comprises 20-90, preferably 40-70, per cent by weight of monomer and when the molecular weight of the monomer is at most 1000

The binder composition according to the present invention comprises, besides disclosed monomer, at least one unsaturated polyester of the type hyperbranched or dendritic macromolecule being chain terminated by at least one unsaturated ester and optionally at least one saturated or unsaturated monofunctional carboxylic acid The chain terminator of said polyester is, in a preferred embodiment, an ester having the general formula

O O

II II

HO - C - R, - C - O - R₂

wherein R, is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or carboxysubstituted variations thereof and wherein R₂ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, whereby at least one substituent R - or R-, comprises at least one aliphatic double bond

The chain terminator of the polyester is in a preferred embodiment an ester of maleic acid, maleic anhydride, fumaric acid, succinic acid or succinic anhydride and 5-methyl- l ,3-dioxane-5-methanol, 5 -ethyl- 1 , 3 -dioxane- 5 -methanol, trimethylol¬ propane diallyl ether, pentaerythritol triallyl ether and/or a lower alcohol such as methanol, ethanol, butanol or propanol at a molar ratio acid to alcohol of 1 0 8 to 1 : 1.2. It is also possible and in certain embodiments suitable to chain terminate the polyester by a complete or partial allylation, by reaction with for instance allylchloride and/or allylbromide, of its terminal hydroxyl groups

The acid is, in an embodiment of the present invention, according to which the chain terminator is a monofunctional carboxylic acid, preferably acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, trimethylacetic acid, crotonic acid, acrylic acid, methacrylic acid, benzoic acid, para-tert.butylbenzoic acid, capric acid, caprylic acid, caproic acid, heptanoic acid, 2-ethylhexanoic acid, pelargonic acid, isononanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, lignoceric acid, montanoic acid, sorbic acid, abietic acid, oleic acid, ricinoleic acid, linoic, linoleic acid, soybean fatty acid, linseed fatty acid, dehydrated castor fatty acid, tall oil fatty acid, tung oil fatty acid, sunflower fatty acid, safflower fatty acid and/or 2,2-dimethylolpropionic acid diallyl ether

The binder composition according to the present invention comprises, besides monomer and polyester, preferably one or more crossiinking catalysts, crossiinking initiators and/or similar additives, each in an amount of 0. 1 -15, preferably 1 - 10, per cent by weight calculated on included polyester. Crossiinking catalysts and crossiinking initiators are suitably

(a) benzoephenones such as alkyl and haloalkylbenzoephenones,

(b) antraquinones such as nitroantraquinones, antrahydroquinones and derivatives thereof,

(c) benzoin and derivatives thereof,

(d) acetophenone and derivatives thereof,

(e) acyloxime esters and derivatives thereof,

(f) benzil ketals and derivatives thereof,

(g) peroxides such as hydrogen peroxide, methylethylketone peroxide, methyliso- butylketone peroxide, cumenhydroperoxide and benzoyl peroxide,

(h) metal salts such as octoates, naphthenates and oleates of cobalt and manganese, (i) perbenzoates such as alkylperbenzoates, (j) cathecols such as alkylcathecols and/or (k) phenylamines such as aniline, alkylanilines, toluidine and alkyltoluidines.

The binder composition constitutes in various embodiments 1 - 100, preferably 20- 100 and most preferably 50- 100, per cent by weight of an air drying, heat curing or radiation curing paint or lacquer intended for industrial surface treatment of for instance paper, wood, plastics and/or steel, such as a printing ink, a furniture coating, an automotive coating, a coating for domestic appliances or a microlithographic resist/coating

The binder composition can, furthermore, advantageously be included in or be an adhesive

The monomer included in the binder composition according to the present invention is especially suitable for use with dendritic or hyperbranched macromolecules, but provides excellent results with all types of unsaturated polyesters substituting or supplementing various vinyl and acrylic monomers

The present invention will now be further disclosed by means of enclosed embodiment examples 1 -22, wherein the examples disclose

Example 1 Preparation of a 2-generation hyperbranched polyester

Example 2 Preparation of an alkyl terminated saturated polyester from the product obtained in Example 2 Example 3 Preparation of a carboxyfunctional ester of trimethylolpropane diallyl ether and maleic anhydride Example 4 Preparation of a carboxyfunctional ester of trimethylolpropane diallyl ether and succinic anhydride Example 5 Preparation of a carboxyfunctional ester of maleic anhydride and ethanol Example 6 Preparation of an unsaturated polyester from the products obtained in Examples 2 and 3 Example 7 Preparation of an unsaturated polyester from the products obtained in Examples 2 and 4 Example 8 Preparation of an unsaturated polyester from the products obtained in Examples 2 and 5 Example 8 Preparation of an ester of trimethylolpropane diallyl ether and succinic anhydride Example 10 Binder composition comprising the products obtained in Examples

3, 5 and 6 Example 1 1 Binder composition comprising the products obtained in Examples

3, 5 and 7 Example 12 Binder composition comprising the products obtained in Examples

3, 5 and 8 Examples 13- 1 5 Binder compositions comprising the products obtained in

Examples 3, 5 and 9 Example 16 Evaluation in lacquers of the binder compositions according to

Examples 1 - 1 5 Example 17 Preparation of an alkyl terminated saturated polyester from the product obtained in Example 1 Example 1 8 Preparation of an unsaturated polyester from the products obtained in Examples 3 and 17 Examples 19-20 Binder compositions comprising the products obtained in

Examples 3 , 5 and 18 Example 21 Evaluation in lacquers of the binder compositions according to

Examples 19 and 20 Example 22 Evaluation in UV curing lacquers of the binder compositions according to Examples 1 1 and 14 The invention is not limited to shown embodiments as these with regard to for instance the molecular composition of the monomer as well as the polyester, degree of unsaturation and hence the binder composition, can be modified within the scope of the invention

Example 1

308 9 g (0 85 mole) Polyol PP 50 (ethoxylated pentaerythritol, Perstorp Polyols), 460 5 g (3 42 moles) of 2,2-dimethylolpropιonic acid and 0 46 g (0 004 mole) H₂SO₄ (96%) were charged in a 4-necked reaction flask provided with a stirrer, cooler, manometer and distillation receiver The equipment was furthermore connected to a vacuum pump The mixture was heated to 120°C, whereby water formation commenced and 2,2-dimethylolpropionic acid began to melt The temperature was after 20 minutes 140°C and a clear solution was obtained The pressure was reduced from atmospheric pressure to 20-30 mm Hg and the reaction was allowed to continue under heavy stirring for 240 minutes until an acid value of 7 0 mg KOH/g was obtained 460 5 g (6 84 moles) of 2,2-dimethylolpropionic acid and 0 7 g (0 007 mole) of H₂SO₄ (96%) was added to the reaction mixture during 10 minutes A clear solution was after a further 25 minutes obtained, whereby the pressure once again was reduced to 20-30 mm Hg and the reaction allowed to continue for 210 minutes until an acid value of 10 2 mg KOH/g was obtained

Obtained hyperbranched polyester was analysed with regard to hydroxyl value and molecular weight The result is given below

Acid value, mg KOH/g 10 2

Hydroxyl value, mg KOH/g 500

Theoretical hydroxyl value, mg KOH/g 51 1

Molecular weight, g/mole 1824

Theoretical molecular weight, g/mole 1748 Example 2

830 0 g of the hyperbranched polyester obtained in Example 1 , 677 7 g (4 59 moles) of a mixture of caprylic and capric acid, 2 0 g (0 03 mole) of Ca(OH)₂ and 75 g of xylene were charged in a 4-necked reaction flask provided with a stirrer, nitrogen inlet, a Dean-Stark receiver and a cooler The reaction mixture was during 50 minutes heated to 170°C, whereby water began to evaporate The reaction mixture was now during 120 minutes heated from 170°C to 210°C, corresponding to a temperature gradient of 0 3°C/minute The reaction was under stirring allowed to continue for 510 minutes until an acid value of 5 6 mg KOH/g was obtained Xylene was removed by applying full vacuum for approx 20 minutes Obtained product was analysed with regard to acid value, hydroxyl value, viscosity, non-volatile content and colour The result is given below

Final acid value, mg KOH/g 4 2

Hydroxyl value, mg KOH/g 1 1 1

Theoretical hydroxyl value, mg KOH/g 1 1 1

Viscosity, 23°C, mPas- 16200

Non-volatile content, % 99 3

Colour, Gardner 4

Example 3

502.2 g (2 30 moles) of trimethylolpropane diallyl ether and 202 9 g (2 07 moles) of maleic anhydride were charged in a 4-necked reaction flask provided with a magnetic stirrer, nitrogen inlet and a cooler The reaction mixture was during 120 minutes heated to 82°C, whereby an exothermic reaction was observed The solution was, when the exotherm had decreased, heated to 90°C and kept at this temperature for 120 minutes and then cooled

Analysis of obtained ester/monomer gave the following values

Acid value, mg KOH/g 169

Theoretical acid value, mg KOH/g 165

Viscosity, 23°C, mPas 127

Colour, Gardner < 1 Example 4

502 2 g (2 30 moles) of trimethylolpropane diallyl ether and 207 0 g (2 07 moles) of succinic anhydride were charged in a 4-necked reaction flask provided with a magnetic stirrer, nitrogen inlet and a cooler The reaction mixture was during 120 minutes heated to 130°C and kept at this temperature for 120 minutes and then cooled

Analysis of obtained ester/monomer gave the following values

Acid value, mg KOH/g 164

Theoretical acid value, mg KOH/g 164

Viscosity, 23°C, mPas 124

Colour, Gardner 1

Example 5

506 0 g ( 1 1 00 moles) of ethanol and 215 6 g (2 20 moles) of maleic anhydride were charged in a 4-necked reaction flask provided with a magnetic stirrer, nitrogen inlet and a cooler The reaction mixture was during 120 minutes heated to 80°C and kept at this temperature for 100 minutes, whereafter excess of ethanol was evaporated by vacuum distillation

Analysis of obtained ester/monomer gave the following values

Acid value, mg KOH/g 368

Theoretical acid value, mg KOH/g 390

Viscosity, 23°C, mPas 46

Colour, Gardner < 1

Example 6

400 0 g of the polyester according to Example 2, 1 74 6 g of the ester according to Example 3 , 1 4 g (0 014 mole) of H₂SO₄ (96%) and 57 g of heptane were charged in a 4-necked reaction flask provided with a stirrer, nitrogen inlet, a Dean-Stark receiver and a cooler The reaction mixture was during 45 minutes heated to 120°C, whereby water began to evaporate The reaction was under stirring at 120°C allowed to continue for 780 minutes until an acid value of 10 0 mg KOH/g was obtained 3 0 g of Ca(OH)₂ was now added and heptane removed by applying full vacuum for approx. 20 minutes, whereafter obtained product was pressurised and filtered

Obtained hyperbranched unsaturated polyester was analysed with regard to acid value, viscosity, non-volatile content and colour The result is given below

Final acid value, mg KOH/g: 8 5

Viscosity, 23°C, mPas 26900

Non-volatile content, %. 95 9

Colour, Gardner 4-5

Example 7

400.0 g of the polyester according to Example 2, 1 80 0 g of the ester according to Example 4, 1 .4 g (0.014 mole) of H₂SO₄ (96%) and 58 g of heptane were charged in a 4-necked reaction flask provided with a stirrer, nitrogen inlet, a Dean-Stark receiver and a cooler. The reaction mixture was during 30 minutes heated to 120°C, whereby water began to evaporate. The reaction was under stirring at 120°C allowed to continue for 390 minutes until an acid value of 8 1 mg KOH/g was obtained. 3.0 g of Ca(OH)₂ was now added and heptane removed by applying full vacuum for approx. 20 minutes, whereafter obtained product was pressurised and filtered.

Final acid value, mg KOH/g 4 9

Viscosity, 23°C, mPas: 13800

Non-volatile content, %: 96 8

Colour, Gardner 5

Example 8

400.0 g of the polyester according to Example 2, 80 2 g of the ester according to Example 5, 1 .4 g (0. 14 mole) of H₂S0₄ (96%) and 48 g of heptane were charged in a 4-necked reaction flask provided with a stirrer, nitrogen inlet, a Dean-Stark receiver and a cooler. The reaction mixture was during 20 minutes heated to 120°C, whereby water began to evaporate The reaction was under stirring at 120°C allowed to continue for 165 minutes until an acid value of 24 7 mg KOH/g was obtained. 3.0 g of Ca(OH)₂ was now added and heptane removed by applying full vacuum for approx. 20 minutes, whereafter obtained product was pressurised and filtered

Final acid value, mg KOH/g 20 8

Viscosity, 23°C, mPas: 30000

Non-volatile content, %: 93 9

Colour, Gardner. 4

Example 9

61 1 .3 g (2 80 moles) of trimethylolpropane diallyl ether, 1 33 0 g ( 1 33 mole) of succinic anhydride and 37 g of toluene were charged in a 4-necked reaction flask provided with a stirrer, nitrogen inlet, a Dean-Stark receiver and a cooler The reaction mixture was during 30 minutes heated to 130°C and 0 7 g (0.007 mole) H₂SO₄ (96%) charged The solution was during a further 5 minutes heated until a temperature of 160°C was obtained and water began to evaporate The reaction was allowed to continue at this temperature for 155°C until an acid value of 6.2 mg KOH/g was obtained. 2.0 g Ca(OH)₂ was now added and toluene removed by applying full vacuum for approx. 20 minutes, whereafter obtained product was pressurised and filtered.

Obtained polyester/monomer was analysed with regard to acid value, viscosity and colour. The result is given below

Final acid value, mg KOH/g: 5 9

Viscosity, 23°C, mPas: 58

Colour, Gardner 2-3

Example 10

The products prepared according to Examples 3, 5 and 6 were mixed giving the following composition by weight

Unsaturated polyester according to Example 6 21 .0%

Monomer according to Example 3 : 39.9%

Monomer according to Example 5 : 39. 1 %

Obtained binder composition exhibited a viscosity of 190 mPas at 25°C Example 11

The products prepared according to Examples 3, 5 and 7 were mixed giving the following composition by weight

Unsaturated polyester according to Example 7 17 7%

Monomer according to Example 3 40 8%

Monomer according to Example 5 41 5%

Obtained binder composition exhibited a viscosity of 130 mPas at 25°C

Example 12

The products prepared according to Examples 3, 5 and 8 were mixed giving the following composition by weight

Unsaturated polyester according to Example 8 1 5 7%

Monomer according to Example 3 38 0%

Monomer according to Example 5 46 3%

Obtained binder composition exhibited a viscosity of 130 mPas at 25°C

Example 13

The products prepared according to Examples 5, 7 and 9 were mixed giving the following composition by weight

Unsaturated polyester according to Example 7 20 0%

Monomer according to Example 9 28 9%

Monomer according to Example 5 5 1 1 %

Obtained binder composition exhibited a viscosity of 90 mPas at 25°C

Example 14

The products prepared according to Examples 5, 7 and 9 were mixed giving the following composition by weight Unsaturated polyester according to Example 7 40 0%

Monomer according to Example 9 1 7 7%

Monomer according to Example 5 42 3%

Obtained binder composition exhibited a viscosity of 270 mPas at 25°C

Example 15

Unsaturated polyester according to Example 7 60 0%

Monomer according to Example 9 6 6%

Monomer according to Example 5 33 4%

Obtained binder composition exhibited a viscosity of 820 mPas at 25°C

Example 16

Lacquers were, from the binder compositions according to Examples 10- 1 5, prepared giving the following composition

Composition according to Example 10- 15 100 00 g Cobalt octoate, 10% Co 1 00 g Dimethyl-/?-toluidine, 10% 2 80 g Butylperbenzoate 2 70 g Methylethylketone peroxide, 50% 2 70 g Levelling agent (BYK 320) 0 40 g

Obtained lacquers were at a filmthickness of 35 ± 5 μm, calculated as dry film, coated on glass panels and cured at 100°C

The result is given in tables below

Properties:

Lacquer according to Example 10 1 1 12 13 14 15

Viscosity, 25°C, mPas 190 130 120 90 270 820 Non-volatile content, % 100 100 100 100 100 100 Curing at 100°C (pendulum hardness according to Kδnig):

Lacquer according to Example 10 11 12 13 14 15

10 min , Konig seconds 36 39 34 17 15 15

20 min , Konig seconds 108 111 99 74 24 17

30 min , Konig seconds 111 113 109 81 25 17

40 min , Konig seconds 118 120 116 85 27 17

50 min , Konig seconds 127 123 116 91 27 17

Example 17

535 5 g of the hyperbranched polyester obtained in Example 1 , 1 75 4 g (2 36 moles) of propionic acid and 75 g of xylene were charged in a 4-necked reaction flask provided with a stirrer, nitrogen inlet, a Dean-Stark receiver and a cooler The reaction mixture was during 25 minutes heated to 1 30°C, whereby water began to evaporate The reaction was allowed to continue at this temperature for 360 minutes until an acid value of 1 1 6 mg KOH/g was obtained Xylene was now removed by applying full vacuum for approx 20 minutes

Obtained alkyl terminated hyperbranched polyester was analysed with regard to acid value, hydroxyl value and non-volatile content The result is given below

Final acid value, mg KOH/g 20 6 Hydroxyl value, mg KOH/g 225 Theoretical hydroxyl value, mg KOH/g 204 Non-volatile content, % 99 7

Example 18

250 0 g of the polyester obtained in Example 17, 278 9 g of the ester obtained in Example 3 , 0 35 g (0 003 mole) of H₂SO₄ (96%) and 50 g of toluene were charged in a 4-necked reaction flask provided with a stirrer, nitrogen inlet, a Dean-Stark receiver and a cooler The reaction mixture was during 50 minutes heated to 130°C, whereby water began to evaporate The reaction mixture was under stirring at 130°C allowed to continue for 300 minutes until an acid value of 26 0 mg KOH/g was obtained 3 0 g Ca(OH)-, was now added and toluene removed by applying full vacuum for approx 20 minutes, whereafter obtained product was pressurised and filtered Obtained hyperbranched unsaturated polyester was analysed with regard to acid value, hydroxyl value, non-volatile content and colour The result is given below

Final acid value, mg KOH/g 25 2

Non-volatile content, %. 98 9

Colour, Gardner 3-4

Example 19

The products prepared according to Examples 3, 5 and 18 were mixed giving the following composition by weight

Unsaturated polyester according to Example 18 62 1 %

Monomer according to Example 3 20 6%

Monomer according to Example 5 1 7 3%

Obtained binder composition exhibited a viscosity of 1900 mPas at 25°C

Example 20

The products prepared according to Examples 3 , 5 and 18 were mixed giving the following composition by weight.

Unsaturated polyester according to Example 1 8 36 3%

Monomer according to Example 3 30 2%

Monomer according to Example 5 33 5%

Obtained binder composition exhibited a viscosity of 400 mPas at 25°C

Example 21

Lacquers were, from the binder compositions according to Examples 19 and 20, prepared giving the following composition

Composition according to Example 19-20 100 00 g

Cobalt octoate, 10% Co 1 00 g

Dimethyl- -toluidine, 10% 2 80 g

Butylperbenzoate 2 70 g

Methylethylketone peroxide, 50% 2 70 g

Levelling agent (BYK 320). 0 40 g Obtained lacquers were at a filmthickness of 35 ± 5 μm, calculated as dry film, coated on glass panels and cured at 1 00°C

The result is given in tables below.

Properties:

Lacquer according to Example 19 20

Viscosity, 25°C, mPas 190 130 Non-volatile content, % 100 100

Curing at 100°C (pendulum hardness according to Konig):

Lacquer according to Example 19 20

10 min , K nig seconds 57 66

20 min., Konig seconds 70 87

30 min., Kόnig seconds 91 91

40 min. , Kόnig seconds 1 1 5 106

50 min., Kόnig seconds 92 1 1 1

Example 22

UV (ultraviolet) curing lacquers were, from the products according to Examples 1 1 and 14, prepared giving the following composition

Composition according to Example 1 1 or 14. ; 00 00 g Photoinitiator (Darocure 1 173): 4 00 g

The lacquers were at a filmthickness of 30 ± 5 , calculated as dry film, coated on glass panels and curing by means of an equipment comprising a UV-lamp, having an effect of 80 W/cm, and conveyor belt, having a belt speed of 12 5 m/minute The result is given in tables below.

Properties:

Lacquer according to Example 1 1 14

Viscosity, 25°C, mPas 130 270 Non-volatile content, % 100 1 00

UV curing - Number of passages under the UV lamp (pendulum hardness according to Kδnig):

Lacquer according to Example 1 1 14

8 passages, Kόnig seconds 13 1 1 16 passages, Kόnig seconds 27 2 1

Claims

1. A binder composition comprising at least one unsaturated monomer, at least one unsaturated polyester and preferably one or more crossiinking catalysts and/or crossiinking initiators and/or similar additives, whereby unsaturation within the monomer can be crosslinked with unsaturation within the polyester c h a r a c t e r i s e d i n, a) that the monomer is i) an ester of at least one di, tri or polyfunctional aliphatic, cycloaliphatic or aromatic carboxylic acid or, where applicable, corresponding anhydride and at least one monofunctional aliphatic, cycloaliphatic or aromatic alcohol, ii) an ester of at least one linear aliphatic monofunctional carboxylic acid having more than 3 carbon atoms, a branched aliphatic monofunctional carboxylic acid having more than 4 carbon atoms, a cycloaliphatic or aromatic monofunctional carboxylic acid and at least one mono, di, tri or polyfunctional aliphatic, cycloaliphatic or aromatic alcohol, iii) an ester of a linear aliphatic monofunctional carboxylic acid having more than 3 carbon atoms, a branched aliphatic monofunctional carboxylic acid having more than 4 carbon atoms, a cycloaliphatic or aromatic monofunctional carboxylic acid and a monofunctional aliphatic, cycloaliphatic or aromatic alcohol, iv) a carboxyfunctional allyl ether or an ester thereof, v) an adduct between at least one carboxyfunctional compound according to (i) or (iv) and at least one di, tri or polyfunctional aliphatic, cycloaliphatic or aromatic alcohol, and/or vi) an adduct between at least one hydroxyfunctional compound according to (ii) or (iv) and at least one di, tri or polyfunctional aliphatic, cycloaliphatic or aromatic carboxylic acid or, where applicable, corresponding anhydride, whereby the unsaturation within the monomer is derived from a carboxylic acid, an anhydride, an allyl ether and/or an alcohol; and b) that the polyester is a dendritic or hyperbranched macromolecule comprising a nucleus having at least one reactive hydroxyl or epoxide group to which 1 - 100, preferably 1 -20, generations of at least one monomeric or polymeric chain extender having at least two reactive hydroxyl groups and at least one reactive carboxyl group, are added, whereby a hyperbranched or dendritic macromolecule wherein terminal groups substantially are hydroxyl groups is yielded, which macromolecule completely or partially in one or more steps is chain terminated i) by at least one chain terminator being a carboxyfunctional unsaturated ester of at least one di, tri or polyfunctional carboxylic acid or, where applicable, corresponding anhydride and at least one monofunctional alcohol, and/or ii) by a complete or partial allylation of the terminal hydroxyl groups of the macromolecule and optionally iii) by at least one chain terminator being a monofunctional saturated or unsaturated carboxylic acid or, where applicable, corresponding anhydride, whereby the unsaturation within the polyester completely or partially is derived from the chain termination.

2. A binder composition according to claim 1 c h a r a c t e r i s e d i n, that the monomer is of general formula (R, - O - R₄)_n - R₂ - (R₄ - O - R₃)_m wherein n and m independently is 1 , 2 or 3 and wherein R, is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, R, is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, R₃ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof and

O H

II wherein R₄ is C or C H whereby at least one substituent R, , R₂ or R₃ comprises at least one aliphatic double bond

3. A binder composition according to claim 2 c h a r a c t e r i s e d i n, that

O

II

R₄ is C and R₂ is carboxysubstituted alkyl, alkenyl alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof

4. A binder composition according to claim 3 c h a ra c t e r ised i n, that

R_j is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or hydroxysubstituted variations thereof O O

II II

R₃ is R₅ - O - C - R₆ - C - O - R₇ wherein R₅ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, R₆ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or hydroxysubstituted variations thereof and R₇ is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof.

5. A binder composition according to claim 2 c ha ra ct e rised i n, that

R₄ is CH₂ and R₂ is hydroxysubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or carboxysubstituted variations thereof.

6. A binder composition according to claim 5 cha ra cte rised in, that

R_[ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or carboxysubstituted variations thereof, R₃ is R₅ - O - CH₂ - R₆ - CH₂ - O - R₇ wherein R₅ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, R₆ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or carboxysubstituted variations thereof and R₇ is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof.

7. A binder composition according to claim 1 ch a ra c t e rised i n, that the monomer is an ester of maleic acid, maleic anhydride or fumaric acid and trimethylolpropane diallyl ether or pentaerythritol triallyl ether at a molar ratio acid or anhydride to alcohol of 1:0.8 to 1:2.2.

8. A binder composition according to claim 1 c h a rac teri s e d i n, that the monomer is an ester of succinic acid or succinic anhydride and trimethylolpropane diallyl ether or pentaerythritol triallyl ether at a molar ratio acid or anhydride to alcohol of 108 to 122

9. A binder composition according to claim 1 c h a ra cteris e d i n, that the monomer is an ester of maleic acid, maleic anhydride or fumaric acid and 5-methyl-l,3-dioxane-5-methanol or 5-ethyl-l,3-dιoxane-5-methanol at a molar ratio acid or anhydride to alcohol of 108 to 122

10. A binder composition according to claim 1 c h a ra c t e ri s ed i n, that the monomer is an ester of propionic acid, acetic acid, crotonic acid, caprylic acid or capric acid and trimethylolpropane diallyl ether or pentaerythritol triallyl ether at a molar ratio acid to alcohol of 108 to 122

11. A binder composition according to claim 1 c h a ra c t eri s ed i n, that the monomer is an ester of crotonic acid and 5-methyl-l,3- dioxane-5-methanol or 5-ethyl-l,3-dioxane-5-methanol at a molar ratio acid to alcohol of 108 to 1.2.2

12. A binder composition according to claim 1 c h a ra cteri s e d i n, that the monomer is an adduct between a) a monoester of maleic acid, maleic anhydride or fumaric acid and an aliphatic monofunctional alcohol, and b) a diol at a molar ratio ester to diol of 081 to 221

13. A binder composition according to claim 12 c h a ra c t e ri s ed i n, that a) the alcohol is methanol, ethanol, propanol and/or butanol and b) the diol is ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 2-methyl-l,3-propanediol, 2-ethyl-2-butyl-l,3-propanediol, cyclohexanedimethanol, l,3-dioxane-5,5-dimethanol, trimethylolpropane monoallyl ether and/or phenylethylene glycol

14. A binder composition according to claim 1 c h a racteris ed i n, that the monomer is an adduct between a) a monoester of maleic acid, maleic anhydride or fumaric acid and an aliphatic monofunctional alcohol, b) a diol, and c) a monofunctional carboxylic acid at a molar ratio ester to diol to acid of 10808 to 1.121.2

15. A binder composition according to claim 14 c h a racterised i n, that a) the alcohol is methanol, ethanol, propanol and/or butanol, b) the diol is ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 2-methyl-l,3-propanediol, 2-ethyl-2-butyl-l,3-propanediol, cyclohexanedimethanol, l,3-dioxane-5,5-dimethanol, trimethylol¬ propane monoallyl ether and/or phenylethylene glycol, and c) the carboxylic acid is crotonic acid, caprylic acid, capric acid, propionic acid and/or acetic acid

16. A binder composition according to claim 1 c h a ra c te ri sed i n, that the monomer is 2,2-dimethylpropionic acid monoallyl ether or 2,2-dimethylol- propionic acid diallyl ether and/or an ester thereof with trimethylolpropane diallyl ether and/or pentaerythritol triallyl ether at a molar ration of 1:08 to 1:1.2.

17. A binder composition according to claim 1 c h a ra cterised i n, that the monomer is an ester of 2,2-dimethylolpropionic acid monoallyl ether or 2,2-dimethylolpropionic diallyl ether and a diol at a molar ratio of 081 to 2.2:1

18. A binder composition according to claim 17 c h a rac t e rised i n, that the diol is ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 2-methyl-l,3-propanediol, 2-ethyl-2-butyl-l,3-propanediol, cyclohexanedimethanol, l,3-dioxane-5,5-dimethanol, trimethylolpropane monoallyl ether and/or phenylethylene glycol

19. A binder composition according to any of the claims 1-18 c h a ra c t e ris e d i n, that the monomer has a molecular weight being less than or equal to 1000

20. A binder composition according to any of the claims 1-19 c h a ra cterised i n, that the monomer constitutes 20-90, preferably 40-70, per cent by weight of the binder composition

21. A binder composition according to claim 1 c h a ra cteris ed i n, that the polyester is chain terminated by a chain terminating ester of general formula

O O

II II

HO - C - R, - C - O - R₂ wherein R_j is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched and/or carboxysubstituted variations thereof and wherein R₂ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, alkylaryl, alkenylaryl, alkynylaryl and/or branched variations thereof, whereby at least one substituent R, or R₂ comprises at least one aliphatic double bond

22. A binder composition according to claim 1 or 21 c h a ra c t eris ed i n, that the chain terminating ester is an ester of maleic acid, maleic anhydride or fumaric acid and 5-methyl-l,3-dioxane-5-methanol or 5-ethyl-l,3-dioxane- 5-methanol at a molar ratio acid or anhydride to alcohol of 108 to 1 12

23. A binder composition according to claim 1 or 21 c h a ra c t e r is ed i n, that the chain terminating ester is an ester of maleic acid, maleic anhydride or fumaric acid and trimethylolpropane diallyl ether or pentaerythritol triallyl ether at a molar ratio acid or anhydride to alcohol of 108 to 1 12

24. A binder composition according to claim 1 or 21 c h a racte ris ed i n, that the chain terminating ester is an ester of succinic or succinic anhydride and trimethylolpropane diallyl ether or pentaerythritol triallyl ether at a molar ratio acid or anhydride to alcohol of 108 to 1 12

25. A binder composition according to claim 1 or 21 c h a ra c t e ris ed i n, that the chain terminating ester is an ester of maleic acid, maleic anhydride or fumaric acid and methanol, ethanol, propanol or butanol at a molar ratio acid or anhydride to alcohol of 1 :0.8 to 1 : 1.2

26. A binder composition according to claim 1 c h a ra c t erised i n, that the polyester is chain terminated by a complete or partial allylation of the terminal hydroxyl groups by reaction with an allylhalid

27. A binder composition according to claim 26 c h a ra c t eris ed in, that the allylhalid is allylchloride and/or allylbromide

28. A binder composition according to claim 1 c h a ra c t erised i n, that the polyester is chain terminated by at least one chain terminator being a monofunctional carboxylic acid, whereby the carboxylic acid is acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, trimethylacetic acid, crotonic acid, acrylic acid, methacrylic acid, benzoic acid, para-tert.butylbenzoic acid, capric acid, caprylic acid, caproic acid, heptanoic acid, 2-ethylhexanoic acid, pelargonic acid, isononanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, lignoceric acid, montanoic acid, sorbic acid, abietic acid, oleic acid, ricinoleic acid, linoic, linoleic acid, soybean fatty acid, linseed fatty acid, dehydrated castor fatty acid, tall oil fatty acid, tung oil fatty acid, sunflower fatty acid, safflower fatty acid and/or 2,2-dimethylolpropionic acid diallyl ether.

29. A binder composition according to claim 1 c h a ra c t eris ed i n, that the binder composition comprises one or more crossiinking catalysts and/or crossiinking initiators being a) benzoephenones such as alkyl and haloalkylbenzoephenones, b) antraquinones such as nitroantraquinones, antrahydroquinones and derivatives thereof, c) benzoin and derivatives thereof, d) acetophenone and derivatives thereof, e) acyloxime esters and derivatives thereof, f) benzil ketals and derivatives thereof, g) peroxides such as hydrogen peroxide, methylethylketone peroxide, methylisobutylketone peroxide, cumenhydroperoxide and benzoyl peroxide, h) metal salts such as octoates, naphthenates and oleates of cobalt and manganese, i) perbenzoates such as alkylperbenzoates, j) cathecols such as alkylcathecols, and/or k) phenylamines such as aniline, alkylanilines, toluidine and alkyltoluidines.

30. A binder composition according to claim 1 or 29 ch aracterised in, that one or more crossiinking catalysts and/or crossiinking initiators are included, each in an amount of 0.1-15, preferably 1-10, per cent by weight calculated on included polyester.

31. A binder composition according to any of the claims 1-30 c h a ra c t e ri s ed i n, that it constitutes 1-100, preferably 20-100 and most preferably 50-100, per cent by weight of an air drying, heat curing or radiation curing paint or lacquer intended for industrial surface treatment of paper, wood, plastics and/or steel, such as a printing ink, furniture coating, an automotive coating, a coating for domestic appliances or a microlithographic resist/coating.