WO2006045662A1 - Dispersions of sulfonic acid group-containing, unsaturated and amorphous polyesters based on defined dicidol isomers - Google Patents

Abstract

The invention relates to an aqueous dispersion based on a sulfonic acid group-containing, amorphous, unsaturated polyester based on defined dicidol isomers and saturated and/or unsaturated dicarboxylic acids. The invention also relates to a method for producing said dispersion and to its use.

Description

Dispersions of sulphonic acid group-containing, unsaturated and amorphous polyesters based on certain dicidolysis monomers

The invention relates to dispersions sulfonsäuregruppenhaltiger, amorphous, unsaturated polyester based on certain Dicidolisomerer and acids.

Unsaturated polyester resins (UP resins) are known. They are prepared by condensation of saturated and unsaturated dicarboxylic acids or their anhydrides with diols. Their properties are variable over a wide range and depend largely on the nature and proportion of the starting materials.

As a carrier of the polymerizable double bonds usually α, ß-unsaturated acids are used, primarily maleic acid or its anhydride or fumaric acid; Unsaturated diols are of minor importance. The higher the content of double bonds, d. H. the shorter the distance of the double bonds in the chain molecules, the more reactive is the polyester resin. It polymerizes very rapidly with high heat development and high volume shrinkage to a highly crosslinked and therefore relatively brittle end product. For this reason, the reactive double bonds in the polyester molecule are "diluted" by condensing in them saturated aliphatic or aromatic dicarboxylic acids. [UP Als] As the alcohol components, straight-chain and branched diols are used.The individual UP resin types differ not only by the components used for their preparation but also by the ratio of saturated ones to unsaturated acids, which determines the crosslink density in the polymerization, the degree of condensation, ie the molecular weight, the acid and OH number, ie the nature of the end groups in the chain molecules, the monomer content, the type of additives (Ulhnann's Encyclopedia of Industrial Chemistry, VOL A21, pp. 217ff., 1992).

UP resins based on dicidol as diol component are z. B. known from DE 924 889, DE 953 117, DE 22 45 110, DE 27 21 989, EP 114 208, EP 934 988.

Object of the present invention was, from the variety of possibilities and range of variation of the prior art, new sulfonic acid, unsaturated and amorphous polyester resins, which are also water-dispersible and transparent as a solid. The problem was solved as explained now.

The invention relates to an aqueous dispersion based on a sulfonic acid, amorphous, unsaturated polyester resin, wherein the polyester resin is composed of

I. an alcohol component,

II. 20 to 100 mol% of an α, ß unsaturated carboxylic acid component, and 0 to 80 mol% of another carboxylic acid component, and

III. at least one sulfonic acid group-containing component, wherein the alcohol component I from a Dicidolgemisch of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane, where each

Isomers may be contained in a proportion of 20 to 40% in the mixture and the sum of the three isomers is 90 to 100%, and the mixture is at least 10 to 100 mol% in the alcohol component of the polyester, and the aqueous dispersion a) a content of non-volatile constituents of 20% to 60%, b) a solvent content of 0 to 20% by weight, c) a pH of between 5.0 and 9.5, d) a viscosity of 20 ° C. from 20 to 350 mPas, e) a proportion of urethane and / or urea groups of 0 to 15 wt .-%, f) has a content of sulfonic acid groups of 0.25 to 20 wt .-%.

As the alcohol component according to the invention a Dicidolgemisch the isomeric

Compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane and 5,8-bis (hydroxymethyl) tricyclo

[5.2.1.0 ^{2> 6} ] decane, each isomer being present in an amount of 20 to 40% in the Mixture may be contained and the sum of the three isomers 90 to 100%, preferably 95 to 100% results, and the mixture is at least 10% in the alcohol component of the polyester used. The isomer content of the Dicidolgemisches can qualitatively and quantitatively z. B. by GC analysis or quantitatively determined by separation by preparative GC or HPLC and subsequent NMR spectroscopy. All corresponding isomers of the dicidol in the 9-position are just as suitable, but due to the mirror symmetry of the above isomers, as well as the cis and trans isomers, indistinguishable under normal, practical circumstances.

In addition, the Dicidolgemisch may contain up to 10% further isomers of diclidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene. Preferably, the alcohol component consists of 20%, of 50%, preferably 90%, particularly preferably 100% Dicidolgemisch, this more preferably contains 95 to 100% of the above three isomeric compounds.

In addition to the dicidol mixture, the alcohol component may contain further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols. Preferred additional alcohols are ethylene glycol, 1,2- and / or 1,3-propanediol, diethylene, dipropylene, triethylene, tetraethylene glycol, 1,2- and / or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, bisphenol A, B, C, F, norbornylene glycol, 1,4-benzyldimethanol and -ethanol, 2,4-dimethyl-2-ethylhexan-1,3-diol, cyclohexanedimethanol, Glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol used.

The sulfonic acid-containing, unsaturated, amorphous polyester resins according to the invention comprise as starting acid component at least one α, β-unsaturated dicarboxylic acid. The unsaturated polyester resins preferably contain citraconic, fumaric, itaconic, maleic and / or mesaconic acid.

It is also possible to additionally contain aromatic and / or aliphatic and / or cycloaliphatic monocarboxylic acids and / or dicarboxylic acids and / or polycarboxylic acids, such as z. As phthalic acid, isophthalic acid, terephthalic acid, l ^ -Cyclohexandicarbonsäure, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, pyromellitic acid and / or trimellitic acid, isononanoic acid, 2-ethylhexanoic acid. Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, hexahydroterephthalic acid, trimellitic acid, adipic acid and / or azelaic acid.

The carboxylic acid component may consist partially or completely of anhydrides and / or low molecular weight alkyl esters, preferably methyl esters and / or ethyl esters.

In general, the alcohol component is contained in the molar ratio of 0.5 to 2.0 to 1 to the acid component, preferably 0.8 to 1.5 to 1. Particularly preferred is the reaction of the alcohol component in the molar ratio of 1.0 to 1.3 to 1 to the acid component instead.

The incorporation of the sulfonic acid groups in the unsaturated, amorphous polyester is carried out either by the use of sulfonic acid-containing monomer units such. As sulfoisophthalic and / or sulfosuccinic acid in the polyester condensation (variant 1.) or by reacting the hydroxy-functional, unsaturated, amorphous polyester with an isocyanate component and a sulfonic acid containing component containing isocyanate-reactive groups. (Variant 2.).

The polyesters of the invention generally have a content of sulfonic acid groups of 0.25 to 20 wt .-%.

As sulfonic acid group-containing components according to variant 1. mono- and polycarboxysulfonic acids and their salts can be used, such as. As sulfoisophthalic acid, sulfosuccinic acid and salts thereof. In this variant, the proportion of the sulfonic acid-containing component is considered as a further carboxylic acid component of the total acid component II., And may be between 1 and 60 mol%, preferably 2 and 40 mol%. According to variant 2. mono- and Polyhydroxysulfonsäuren, and / or mono- and Polyaminosulfonsäuren and their salts can be used, the z. B. are knotted by means of a suitable di- and / or polyisocyanate to the polyester. Suitable examples here are 1,4-dihydroxybutanesulfonic acid, N- (cyclohexyl) aminosulfonic acid and N- (2-aminoethyl)-2-aminoethanesulfonic acid and salts thereof. 0.2 to 3 mol (based on 1 mol of polyester of I. and II (via Mn)), preferably 0.25 to 2 mol of the sulfonic acid-containing component.

Preferred isocyanates for the attachment of the sulfonic acid component according to variant 2 are aliphatic and / or cycloaliphatic polyisocyanates having an average molecular weight of up to about 1000 g / mol and a mean isocyanate functionality of 2 to 4. These include, for example, simple diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, Ethylcyclohexane diisocyanate, phenylene diisocyanate,

Propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, such as 1,6 Diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonanetriisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane and triisocyanate, undecanediisocyanate and - triisocyanate, dodecandi- and triisocyanates, isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl) methane (H ₁₂ MDI), isocyanatomethylmethylcyclohexyl isocyanate, 2,5 (2,6) -bis (isocyanato-methyl) bicyclo [2.2.1 ] heptane (NBDI), 1,3-

Bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI) and / or their technical mixtures, alone or in admixture.

In addition, it is possible to use polyisocyanates which are obtainable by reaction with bifunctional reaction partners (for example diols, diamines, mono- and / or dihydroxysulfonic acids, mono- and / or diaminosulfonic acids, etc.). Another preferred class of polyisocyanates is the compounds prepared by trimerization, allophanatization, biuretization and / or urethanization of the simple diisocyanates having more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as, for example, IPDI, HDI and / or H ₁₂ MDI with polyhydric alcohols (for example glycerol, trimethylolpropane, pentaerythritol) or polyfunctional polyamines or the triisocyanurates obtained by trimerization of the simple diisocyanates, for example IPDI, HDI and H ₁₂ MDI are available. As representatives of the aromatic polyisocyanates, for example, tetramethylenexylylene diisocyanate (TMXDI), 2,4-diisocyanatotoluene and / or its technical mixtures with 2,6-diisocyanatotoluene and 4,4'-diisocyanatodiphenylmethane and / or its technical mixtures with 2,4'-diisocyanatodiphenylmethane can be used become.

The invention also provides a process for the preparation of aqueous, sulfonic acid-containing, unsaturated, amorphous polyesters. In variant 1, the reaction of the starting components I. to III takes place. at a temperature of 150 to 270 ° C, preferably from 160 to 230 ° C, preferably in an inert gas atmosphere, preferably nitrogen or noble gases, more preferably nitrogen, wherein the inert gas has an oxygen content of less than 50 ppm, preferably less than 20 ppm , by (semi) continuous or discontinuous reaction of the starting alcohols L, -acids II. and sulfonic acid III. in one or more stages and subsequent mixing of the optionally neutralized resin with water.

In variant 2, the reaction of the starting components I and II takes place first at a temperature of from 150 to 270 ° C., preferably from 160 to 230 ° C., preferably in an inert gas atmosphere, preferably nitrogen or noble gases, more preferably nitrogen, where the inert gas has an oxygen content of less than 50 ppm, preferably less than 20 ppm, by (semi) continuous or discontinuous reaction of the starting alcohols I and II acids in one or more stages. Subsequently, the reaction with the sulfonic acid-containing monomer and the di- or polyisocyanates, optionally with the aid of a suitable auxiliary solvent at preferred temperatures below 100 ° C., more preferably below 70 ° C. Optionally, the sulfonic acid group-containing compound is previously reacted with the diisocyanate to form a pre-adduct containing isocyanate groups. As suitable auxiliary solvents low-boiling inert solvents are used, which do not form a miscibility gap with water at least over wide ranges, have a boiling point at atmospheric pressure below 100 ° C and therefore, if desired, by distillation easily to a residual content of less than 2 wt .-% and in particular less than 0.5 Separate wt .-% based on the final dispersion. Suitable solvents of this type are for. As acetone, methyl ethyl ketone or tetrahydro-uranium. Basically suitable are also higher-boiling solvents such. As n-butyl glycol, di-n-butyl glycol and N-methylpyrrolidone, which then remain in the water-dilutable dispersion.

Subsequently, the mixing of the optionally neutralized resin with water.

The neutralization of the resins according to the invention can be carried out with inorganic and / or organic bases, such as. For example, sodium hydroxide, potassium hydroxide, ammonia or organic amines. Preferably used are primary, secondary and / or tertiary amines, such as. For example, ethylamine, propylamine, dimethylamine, dibutylamine, cyclohexylamine, benzylamine, morpholine, piperidine and triethanolamine. Particular preference is given to sodium hydroxide and ammonia and also volatile, tertiary amines, in particular dimethylethanolamine, diethylethanolamine, 2-dimethylamino-2-methyl-1-propanol,

Triethylamine, tripropylamine and tributylamine.

The degree of neutralization is preferably 50 to 130% of the neutralization amount necessary for stoichiometric neutralization.

The sulfonic acid-containing, unsaturated, amorphous polyesters according to the invention may have an acid number between 1 and 200 mg KOH / g, preferably between 1 and 100, more preferably between 10 and 50 mg KOH / g and an OH number between 1 and 200 mg KOH / g, preferably between 1 and 100, more preferably between 10 and 50 mg KOH / g.

In a preferred embodiment 1, the unsaturated polyesters containing sulfonic acid groups according to the invention consist of an alcohol component at least 90%, preferably 95%, particularly preferably 100%, of the dicidol mixture of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane and from fumaric acid and / or maleic acid (anhydride), isophorone diisocyanate (IPDI) and / or hexamethylene diisocyanate (HDI) and / or

Bis (isocyanatomethylcyclohexyl) methane (H ₁₂ MDI), and N- (2-aminoethyl) -2-aminoethanesulfonic acid.

In a further preferred embodiment 2, the polyesters contain the o. G. Starting components as in 1, but in addition further acids selected from adipic acid, dodecanedioic acid and / or phthalic acid (anhydride), wherein the ratio of α, ß-unsaturated to additional acid of 2 to 1 to 1 to 4 may vary. Ratios of about 1 to 1 to 1 to 2 are preferred. These generally have acid numbers of 1 to 200, preferably 1 to 100, particularly preferably 10 to 50 mg KOH / g, OH numbers of 1 to 200, preferably 1 to 100 , particularly preferably 10 to 50 mg KOH / g.

In a preferred embodiment 3, the unsaturated polyesters according to the invention containing sulfonic acid groups consist of an alcohol component having at least 90%, preferably 95%, particularly preferably 100%, of the dicidol mixture of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane,

4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane and from fumaric acid and / or maleic acid (anhydride) and sulfoisophthalic acid and / or sulfosuccinic acid.

In a further preferred embodiment 4, the polyesters contain the starting components as in 3, but in addition further acids selected from adipic acid, dodecanedioic acid and / or phthalic acid (anhydride), wherein the ratio of α, ßunsaturated to additional acid of 2 to 1 to 1 can vary to 4. Ratios of about 1 to 1 to 1 to 2 are preferred.

The novel dispersions sulfonsäuregruppenhaltiger, unsaturated, amorphous Polyesters can also auxiliaries and additives selected from inhibitors, organic solvents, surface-active substances, neutralizing agents, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and - initiators, additives for influencing theological properties such. As thixotropic and / or thickening agents, leveling agents, anti-skinning agents, plasticizers, defoamers, antistatic agents, lubricants, wetting and dispersing agents, preservatives such. As well as fungicides and / or biocides, thermoplastic additives, dyes, pigments, matting agents, fire protection equipment, internal release agents, fillers and / or propellants.

In addition, the invention provides the use of the aqueous dispersions sulfonsäuregruppenhaltiger, unsaturated, amorphous polyester.

The aqueous dispersions are used as the main component, base component or additional component in aqueous coating materials, adhesives, gelcoats, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealants and insulating materials; - As the main component, base component or additive component in aqueous putties, primers, fillers, basecoats, topcoats and clearcoats; as main component, base component or additional component in aqueous coating materials, adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealants and insulating materials, further polymers selected from the group of polyurethanes, polyesters, polyacrylates, polyolefins, Natural resins, epoxy resins, silicone oils and resins, amine resins, fluorine-containing polymers and their derivatives are contained alone or in combination.

Articles produced and / or finished with an aqueous, sulfonic acid-containing, amorphous, unsaturated polyester resin are likewise provided by the invention.

The novel aqueous dispersions of sulfonic acid-containing, unsaturated, amorphous polyesters are further illustrated by the following example without the Restrict scope:

example

The starting component dicidol was used in the isomer ratio of approximately 1: 1: 1.

1.25 mol of adipic acid with 3.675 mol of dicidol at max. 210 ° C in a nitrogen atmosphere until an acid number below 5 mg KOH / g is reached. Then 1.25 moles of fumaric acid and 0.05% by weight of hydroquinone monomethyl ether (based on fumaric acid) are added. After stirring for 2 h, a vacuum of 20 mbar is applied until an acid number of less than 5 mg KOH / g is reached. The polyester is dissolved after cooling 60% in acetone.

1128 g of this polyester solution are reacted with 444 g of isophorone diisocyanate in the presence of 1.2 g of dibutyltin dilaurate for 3 hours at reflux temperature until an NCO content of about 1.2% is reached.

The adduct described above is provided with 432 g of a 50% aqueous solution of the sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid and reacted at reflux temperature until an NCO content is below 0.1%.

Desalted water is added with vigorous stirring and, after a further 30 minutes, the acetone is distilled off in a slight vacuum. A storage-stable, solvent-free, cloudy dispersion having a solids content of about 33% is obtained. Key data: Viscosity _D = 200: 260 mPas, pH value: 7, 1.

Key figures after storage

Claims

claims: 1. Aqueous dispersion based on a sulfonic acid, amorphous, unsaturated polyester resin, wherein the polyester resin is composed of I. an alcohol component, II. 20 to 100 mol% of an α, ß unsaturated carboxylic acid component, and 0 to 80 mol% of another carboxylic acid component, and III. at least one sulfonic acid group-containing component, wherein the alcohol component I from a Dicidolgemisch of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane, 4,8- Bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane, each containing isomers in a proportion of 20 to 40% in the mixture and the sum of the three isomers is 90 to 100%, and the mixture is at least 10 to 100 mol% in the alcohol component of the polyester, and the aqueous dispersion a) has a non-volatile content of 20% to 60% , b) a solvent content of 0 to 20% by weight, c) a pH of between 5.0 and 9.5, d) a viscosity at 20 ° C. of 20 to 350 mPas, e) a proportion of urethane and / or urea groups from 0 to 15 wt .-%, f) has a content of sulfonic acid groups from 0.25 to 20 wt .-%. 2. Aqueous dispersion according to claim 1, characterized in that in the alcohol component I. up to 10% further isomers of the dicidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene are included. 3. Aqueous dispersion of a sulfo-containing, amoφhen, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the alcohol component I. further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols. 4. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to claim 3, characterized in that as further alcohols ethylene glycol, 1,2- and / or 1,3-propanediol, diethylene, Dipropylene, triethylene, tetraethylene glycol, 1,2- and / or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol bisphenol A, B, C, F, norbornylene glycol, 1,4-benzyldimethanol and ethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol. 5. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the alcohol component I. is at least 20% of the isomers of the dicidol. 6. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the alcohol component I. consists of at least 50% of the isomers of the dicidol. 7. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized that the alcohol component I. consists of at least 90% of the isomers of the dicidol. 8. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the alcohol component I. consists of 100% of the isomers of the dicidol. 9. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the carboxylic acid component II. Partly or wholly of anhydrides and / or Alkyl esters. 10. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated Polyester resin according to at least one of the preceding claims, characterized in that as α, ß-unsaturated carboxylic acid component II. Citracon-, fumaric, itaconic, maleic and / or mesaconic acid is included. 11. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that as the α, ß-unsaturated carboxylic acid component II. Fumaric acid and / or maleic acid (anhydride) is included. 12. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the further carboxylic acid component aromatic and / or aliphatic and / or cycloaliphatic monocarboxylic acids and / or dicarboxylic acids and / or Contains polycarboxylic acids. 13. Aqueous dispersion of a sulphonic acid-containing, amorphous, unsaturated polyester resin according to claim 12, characterized in that phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, ethyltetra-, methylhexahydrophthalic acid, Hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, pyromellitic acid and / or trimellitic acid whose acid anhydrides and / or methyl esters, isononanoic acid and / or 2-ethylhexanoic acid is contained. 14. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that as further carboxylic acid component of the unsaturated, amorphous polyester Adipic acid and / or dodecanedioic acid and / or phthalic acid (anhydride) is included. 15. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that as component III. Mono- and / or Polycarboxylatosulfonsäuren and / or their salts are included. 16. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to claim 15, characterized in that sulfoisophthalic acid and / or sulfosuccinic acid and / or salts thereof are included. 17. Aqueous dispersion of a sulfonic acid group-containing, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that as component III. the reaction product of hydroxy and / or amine sulfonic acids and a di- and / or polyisocyanate is used. 18. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least the preceding claim, characterized in that 1,4-Dihydroxybutansulfonsäure, N- (cyclohexyl) aminosulfonic acid and / or N- (2-aminoethyl) - 2-aminoethansulfonsäure and / / or their salts are used. 19. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that an aromatic, aliphatic and / or cycloaliphatic diisocyanate is used as the diisocyanate. 20. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that as diisocyanate isophorone diisocyanate and / or hexamethylene diisocyanate and / or 4,4'-Methylenbis (cyclohexyl diisocyanate) is used. 21. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the alcohol component I. of the unsaturated, amorphous polyester in a molar ratio of 0.5 to 2.0 to 1 to the acid component II is. 22. Aqueous dispersion of a sulfonic acid-containing, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the alcohol component I of the unsaturated, amorphous polyester is contained in a molar ratio of 0.8 to 1.5 to 1 to the acid component II. 23. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the alcohol component I. of the unsaturated, amorphous polyester in a molar ratio of 1.0 to 1.3 to 1 to the acid component II is. 24. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated Polyester resin according to at least one of the preceding claims, characterized in that it has an acid number between 1 and 200 mg KOH / g, preferably between 1 and 100, especially between 10 and 50 mg KOH / g. 25. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that it has an OH number between 1 and 200 mg KOH / g, preferably between 1 and 100, particularly preferably between 10 and 80 mg KOH / g. 26. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that auxiliaries and additives are included. 27. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that auxiliaries and additives selected from inhibitors, organic solvents, surface-active substances, neutralizing agents, oxygen and / or Radical scavengers, catalysts, light stabilizers, color brighteners, additives for influencing theological properties such. As thixotropic and / or thickening agents, defoamers, wetting and dispersing agents, preservatives such. As well as fungicides and / or biocides are included. 28. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the alcohol component of the unsaturated amorphous polyester from at least 90% of the isomers of the diclidol and the acid component of fumaric acid and / or Maleic acid (anhydride) exists. 29. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to claim 28, characterized in that in the amorphous, unsaturated polyester additionally adipic acid, dodecanedioic acid and / or phthalic acid (anhydride) are contained as the acid component in a ratio α, ß-unsaturated to the additional acid from 3 to 1 to 1 to 4, preferably from 1 to 1 to 1 to 2. 30. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that at least a part of the acid groups of the sulfonic acid-containing unsaturated, amorphous polyester are neutralized. 31. Aqueous dispersion of a sulfonic acid, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that an amine and / or an inorganic alkali is used for neutralization. 32. Aqueous dispersion of a sulphonic acid-containing, amorphous, unsaturated polyester resin according to at least one of the preceding claims, characterized in that the degree of neutralization between 0.3 and 1.2, preferably between 0.5 and 1.0, particularly preferably between 0.6 and 1.0 is. 33. A process for the preparation of aqueous, sulfonic acid, unsaturated, amorphous polyesters, according to at least one of claims 1 to 32, a) by (semi) continuous or discontinuous reaction of the starting components at a temperature of 150 to 270 ° C, preferably 160 to 230 ° C in inert gas atmosphere and disperse in water, optionally after neutralization. b) by (semi) continuous or discontinuous reaction of the starting components I. and II. At 150 to 270 ° C, preferably 160 to 230 ° C, preferably in an inert gas atmosphere and subsequent reaction with the sulfonic acid-containing monomer and the di- or polyisocyanates optionally under With the aid of a suitable auxiliary solvent at preferred temperatures below 100 ° C, more preferably below 70 ° C and subsequent mixing of the optionally neutralisiserten resin with water. 34. A process for the preparation of an aqueous dispersion according to claim 33, characterized in that the amorphous unsaturated polyester containing sulfonic acid groups is dispersed in the melt or in water using an auxiliary organic solvent. 35. A process for preparing an aqueous dispersion according to claims 33 and 34, characterized in that the organic auxiliary solvent is distilled off. 36. Use of an aqueous dispersion according to at least one of the preceding claims, as a main component, base component or additive component in aqueous coating materials, adhesives, gelcoats, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealants and insulating materials. 37. Use of an aqueous dispersion according to at least one of the preceding claims, as the main component, base component or additional component in aqueous putties, primers, fillers, basecoats, topcoats and clearcoats. 38. Use of an aqueous dispersion according to at least one of the preceding claims, for metals, plastics, wood, leather, cardboard, paper, textiles and glass. 39. Use of an aqueous dispersion according to at least one of the preceding claims, as the main component, base component or additional component in aqueous coating materials, adhesives, gel coats, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials, characterized in that further oligomers and / or polymers are contained. 40. Use of an aqueous dispersion according to at least one of the preceding claims, as main component, base component or additional component in aqueous coating materials, adhesives, printing inks and inks, polishes, glazes, Pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials, characterized in that further oligomers and / or polymers selected from the group of polyurethanes, polyesters, polyacrylates, polyethers, Polyolefϊne, natural resins, epoxy resins, silicone oils and resins, amine resins, fluorine-containing Polymers and their derivatives are contained alone or in combination. 41. Use of an aqueous dispersion according to at least one of the preceding claims, as main component, base component or additive component in aqueous coating materials, adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials, characterized in that Auxiliary and additives are included. 42. Use of an aqueous dispersion according to at least one of the preceding claims, as the main component, base component or additional component in aqueous coating materials, adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, pigment pastes, fillers, cosmetic articles and / or sealants and insulating materials, characterized in that auxiliaries and additives selected from inhibitors, organic solvents, surface-active substances, neutralizing agents, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing theological properties such. As thixotropic and / or thickening agents, leveling agents, Hautverhinderungs¬ agents, plasticizers, defoamers, antistatic agents, lubricants, wetting and dispersing agents, preservatives such. As well as fungicides and / or biocides, thermoplastic additives, dyes, pigments, matting agents, Feuerschutz¬ equipment, internal release agents, fillers and / or propellants are included. 43. Sulfonic acid-containing, amorphous, unsaturated polyester resins, wherein the polyester resin is composed of I. an alcohol component, II. 20 to 100 mol% of an α, ß unsaturated carboxylic acid component, and 0 to 80 mol% of another carboxylic acid component, III. and at least one sulfonic acid group-containing component, wherein the alcohol component I is selected from a mixture of dicidol of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ² ' ⁶ ] decane, 4.8- Bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2> 6} ] decane, each containing isomers in a proportion of 20 to 40% in the mixture and the sum of the three isomers is 90 to 100%, and the mixture is at least 10 to 100 mol% in the alcohol component of the polyester, and the aqueous dispersion a) has a non-volatile content of 20% to 60% , b) a solvent content of 0 to 20% by weight, c) a pH of between 5.0 and 9.5, d) a viscosity at 20 ° C. of 20 to 350 mPas, e) a proportion of urethane and / or urea from 0 to 15% by weight, f) has a content of sulfonic acid groups of 0.25 to 20% by weight. 44. articles, manufactured and / or finished with an aqueous, sulfonic acid, amorphous, unsaturated polyester resin according to any one of the preceding claims.