HRP960567A2 - Polyester-acrylate based binder, process for its preparation and its use - Google Patents

Description

The field of technology

The invention is from the field of polymer and varnish chemistry.

Technical problem

The invention relates to binders based on polyester-acrylate, the process of their production and use.

State of the art

Binders based on polyester-acrylate are common commercial goods. Manufacturers recommend them for the production of topcoats that require the addition of at least one hardener, such as polyisocyanates. These varnishes are air-dried and used for car refinishing. Hardened lacquer films are hard, tough-elastic, high gloss and full, and have good resistance to solvents and gasoline.

Description of the solution to the technical problem with examples

The purpose of the invention is to provide a binder for base coatings and fillers, which is hardened with di and/or polyisocyanates. Furthermore, the binder of the subject invention should be suitable for the production of reactive varnishes for metals, wood, paper, cardboard and glass, as well as for parts of molds made of plastics. The initial polyester-acrylate resin must be dissolved in organic solvents. The solution should have a high content of solid particles ("High Solid") and a very low viscosity. Usable hydroxyl numbers of the binders of the present invention are in the range of 40 to 300 mg KOH/g of solid resin, with values of 50 to 250 KOH/g of solid resin being preferred. Acid numbers are from 3 to 20 mgKOH/g solid resin. In addition, coatings based on polyester-acrylate resins as binders and di- and/or polyisocyanates as crosslinkers and hardeners should dry very quickly in the air, adhere well to all substrates, preferably contain as few organic solvents as possible, so that they are available only covering agents that do not pollute the environment. Furthermore, resistance to corrosion is required. The previously described types of covering agents must have a service life of at least 2 hours.

The upcoming tasks of the invention will be solved according to patent claims from 1 to 25, based on a binder based on polyester-acrylate, which is made of:

And 10 to 90 wt. % of polyester from

a.1) 0 to 63 mol. % neopentylglycol,

a.2) 0 to 45 mol. % trimethylolpropane,

a.3) 10 to 52 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its anhydrides,

a.4) 0 to 32 mol. % phthalic acid and/or its anhydride,

a.5) 0 to 35 mol.% of other alkanediols from the group of 1,2-,1,3-, 1,4-butanediol,

1,5-pentanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, neopentyl ester of hydroxypivalic acid, cyclohexanediol, trimethylpentanediol, ethylbutylpropanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-dipropylene glycol, hexylene glycol individually or in a mixture,

a.6) 0 to 32 mol.% of other dicarboxylic acids and/or hydroxycarboxylic acids and/or their/their anhydrides, and/or from the group of 5-hydroxyisophthalic acid, isophthalic acid, terephthalic acid, halogen acids such as tetrachloro, or tetrabromophthalic acid, tetrahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tricyclodecane-dicarboxylic acid, endoethylenehexahydrophthalic acid, camphoric acid (1,2,2,-trimethylcyclopentane-1,3 -dicarboxylic acid), adipic acid, succinic acid, azelaic acid, sebacic acid, glutaric acid individually or in a mixture,

a.7) 0-16 mol.% of monocarboxylic acids or/and hydrocarbon acids from the group of benzoic acid, p,tert.-benzoic acid, lauric acid, isonanoic acid, 2,2-dimethylpropionic acid, 2-ethylhexanoic acid, caproic acid , caprylic acids, capric acids, versatile acids, hexahydrobenzoic acids, hydroxypivalic acids, 3-,4-hydroxybenzoic acids, 2-hydroxyisobutyric acids, 2-,3,-4,-,2,- hydroxy-3-,4-, 3-,4,-methoxybenzoic acid, 2-,3-hydroxy-4-,4-methylbenzoic acid, 2-,3-,4-hydrophenyl acetic acid, 2-hydroxy-2-phenylpropionic acid, 3-(3- ,4-)-hydroxyphenylpropionic acids, individually or in a mixture.

a.8) 0 to 14 mol.% of aliphatic and/or cycloaliphatic monoalcohols with 4 to 8 atoms, individually or in a mixture, whereby the mol. The percentages specified in a.1), a.3) and possibly in a.2), a.4), a.5), a.6), a.7) and a.8), in certain time replenished to 100 mol.%, and B 90 to 10 wt. % acrylate resin from

b. 1) 5-55 wt.% hydroxyalkyl(meth)acrylate with 2 to 5 C atoms in the hydroxyl residue,

individually or in a mixture,

b.2) 0 to 80 wt.% of aromatic vinyl resins, individually or in a mixture,

b.3) 0 to 95 wt.% alkyl (meth)acrylate with 1 to 9 C atoms in the alkyl residue, individually or in a mixture,

b.4) 0.0 to 6 wt.% (methyl)acrylic acid, individually or in a mixture, whereby the amounts specified in b.l) and possibly b.2), b.3) and/or b.4 are supplemented up to 100 wt.%.

The aforementioned composition of the acrylate resin component B interprets the embodiment l for the acrylate resin component B.

The following procedure for the production of binders based on polyester-acrylate consists of:

A. 10 to 90 wt.% polyester from

a.1) 5 to 63 mol. % neopentylglycol,

a.2) 0 to 45 mol.% trimethylolpropane,

a.3) 15 to 52 mol.% hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its anhydrides, a.4) 0-32 mol.% phthalic acid and/or its anhydride,

a.5) 0 to 18 mol. % of other alkanediols from the group of 1,2-, 1,3-, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane-diol, cyclohexane-1,4-dimethanol, neopentyl ester of hydroxypivalic acid, cyclohexanediol, trimethyl pentadiol, dipropylene glycol, hexylene glycol, individually or in a mixture,

a.6) 0 to 32 mol.% of other dicarboxylic acids and/or hydroxycarboxylic acids and/or its/their anhydrides and/or from the group of 5-hydroxyisophthalic acid, isophthalic acid, terephthalic acid, halogen acids, such as tetrachlorocyclohexanedicarboxylic acid, 1, 4-10cyclohexanedicarboxylic acid, 4-dicarboxylic acid, endoethylene hexahydrophthalic acid, camphoric acid, azelaic acid, sebacic acid, glutaric acid, individually or in a mixture.

a.7) 0 to 16 mol.% of monocarboxylic acids and/or hydroxycarboxylic acids from the group of benzoic acid, p.tert.-butylbenzoic acid, lauric acid, isonanoic acid, 2,2-dimethylpropionic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, versatilic acid, hexahydrobenzoic acid, hydroxypivalic acid, 3-,4-hydroxybenzoic acid, 2-hydroxyisobutyric acid, 2-,3,-4, -, 2,-hydroxy-3-,4-,3 -,4,-methoxybenzoic acid, 2-,3-hydroxy-4-,4-methylbenzoic acid, 2-,3-,4-hydroxyphenylacetic acid, 2-hydroxy-2-phenylpropionic acid, 3-(3-,4 -)-hydroxyphenylpropionic acid, individually or in a mixture,

a.8) 0 to 14 mol. % of aliphatic and/or cycloaliphatic monoalcohols with 4 to 18 C atoms, individually or in a mixture, whereby the mol. The percentages specified in a.1), a.3) and possibly in a.2), a.4), a.5), a.6), a.7) and a.8) supplement to 100 mol.%, and B 90 to 10 wt.% of acrylate resin according to implementation procedure 1 for the acrylic component of resin B.

Embodiment I for polyester component A

In a special embodiment of the subject invention, the binder contains one polyester component A, obtained by embodiment I, which is the reaction product of neopentylglycol and hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its/their anhydrides. The binder can be produced from:

And 10 to 90 wt.% of polyesters with stoichiometrically calculated molecular masses from 400 to 1300, acid numbers from 5 to 1030 mg KOH/g solid resin and hydroxyl numbers from 70 to 270 mg KOH/g solid resin from

a.1) 53 to 63 mol.% neopentyl alcohol,

a.3) 37 to 47 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, whereby a.1) and a.3) are supplemented up to 100 wt.% and

B 10 to 90 wt.% of acrylate resin according to procedure l for the component of acrylate resin B.

Embodiment 2 for component acrylate resin B

Acrylate resin from

b.1) 5 to 35 wt.% of hydroalkyl(meth)acrylate with 2 to 5 C atoms in the hydroxyalkyl residue, individually or in a mixture,

b.2) 10 to 80 wt.% of aromatic vinyl compounds, individually or in a mixture,

b.3) 0 to 50 wt.% alkyl(meth)acrylate with 1 to 9 C atoms in the alkyl residue, individually or in a mixture,

b.4) 0.0 to 6 wt. % of (meth)acrylic acid, individually or in a mixture, whereby the quantities specified in b.1) b.2) and possibly b.3),) and/or b.4 are supplemented up to 100 wt.%.

In the further execution process, component b.3) is present in the acrylate resin in concentrations of 5 to 30 wt.%.

Embodiment 3 for component acrylate resin B

In the further execution process of 3 components acrylate resin B, partial component b.4), in the embodiment of 2 components acrylate resin B, is additionally present in concentrations of 0.5-3 wt.%.

Preference is given to the polyester-acrylate-based binder recipe using embodiment I for the polyester component A, which is obtained from:

And 10 to 90 wt.% of polyesters with molecular weights between 400 and 1100, acid numbers of 10 to 25 mg KOH/g of solid resin and hydroxyl numbers of 80 to 265 mh KOH/g of solid resin from

a.1) 54 to 62 mol.% neopentylglycol,

a.3) 38 to 46 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides,

B 10 to 90 wt.% acrylate resin from

b.1) 8 to 32 wt.% hydroxyalkyl (meth) acrylate with 2 to 4 C atoms in the hydroxyalkyl residue, individually or in a mixture,

b.2) 20 to 75 wt.% of aromatic vinyl compounds, individually or in a mixture, b.3) 5 to 45 wt.% of alkyl (meth)acrylate with 2 to 6 C atoms in the alkyl residue, individually or in a mixture; b.4) 0.1 to 5 wt.% (meth)acrylic acid, individually or in a mixture.

The following composition of the component acrylate resin B shows embodiment 4 for the acrylate component B.

Preference is given to the binder composition on a polyester-acrylate basis in embodiment I for the polyester component A, which is obtained from:

A. 10 to 90 wt.% polyester from

a.1) 55 to 61 mol.% neopentylglycol,

a.3) 33 to 45 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its/their anhydrides,

B 65 to 80 wt.% acrylate resin from

b.1) 10 to 90 wt.% hydroxyalkyl(meth)acrylate with 2 to 4 C atoms in the alkyl residue, individually or in a mixture,

b.2) 45 to 70 wt. % styrene,

b.3) 10 to 25 wt.% alkyl (meth)acrylate with 2 to 5 C atoms in the alkyl residue, individually or in a mixture,

b.4) 0.5 to 4.0 wt.% (meth) of acrylic acid, individually or in a mixture,

A further binder based on polyester-acrylate is produced from:

A. 10 to 90 wt.% polyester from

a.1) 55 to 61 mol.% neopentylglycol,

a.3) from 39 to 45 mol.% of hexahydrophthalic acid and/or methyl-hexahydrophthalic acid or its/their anhydrides. B 10 to 90 wt.% acrylate resin from

b.1) 5 to 35 wt.% of hydroxyalkyl(meth)acrylate with 2 to 5 C atoms in the hydroxyalkyl residue, individually or in a mixture,

b.2) 30 to 80 wt.% of aromatic vinyl compounds, individually or in a mixture,

b.3) 0 to 30 wt.% alkyl (meth)acrylate with 1 to 9 C atoms in the alkyl residue, individually or in a mixture,

b.4) 0.0 to 5 wt.% (meth)acrylate, individually or in a mixture.

A further embodiment of the invention relates to a binder based on polyester-acrylate produced from:

A. 10 to 90 wt.% polyester from

a.1) from 56 to 60 mol.% neopentylglycol,

a.2) from 40 to 54 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides,

B. 10 to 90 wt.% acrylate resin from

b.1) 8 to 32 wt.% hydroxyalkyl(meth)acrylate with 2 to 4 C atoms in the alkyl residue, individually or in a mixture,

b.2) 40 to 75 wt.% of aromatic vinyl compounds, individually or in a mixture,

b.3) 5 to 28 wt.% alkyl(meth)acrylate with 2 to 6 C atoms in the alkyl residue, individually or in a mixture,

b.4) 0.1 to 4.5 wt.% (meth)acrylic acid, individually or in a mixture.

Another embodiment of the invention relates to a binder based on polyester-acrylate, which is produced from:

A. 10 to 90 wt.% polyester from

a.1) from 56 to 60 mol% of neopentylglycol,

a.2) from 40 to 54 mol% of hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its/their anhydrides,

B. 10 to 90 wt.% acrylate resin from

b.1) 10 to 30 wt.% hydroxyalkyl (meth) acrylate with 2 to 4 C atoms in the hydroxyl residue, individually or in a mixture,

b.2) 45 to 70 wt.% of aromatic vinyl compounds, individually or in a mixture,

b.3) 10 to 25 wt.% alkyl(meth)acrylate with 2 to 5 C atoms in the alkyl residue, individually or in a mixture,

b.4) 0.5 to 4.0 wt.% (methyl) acrylic acid, individually or in a mixture,

b.4) 0.5 to 4.0 wt.% (meth)acrylic acid, individually or in a mixture.

The following composition of the component acrylate resin B is in embodiment 5 for the component acrylate resin B.

Embodiment II for polyester component A

In a further, special embodiment of the invention, the binder contains polyester component A, in embodiment II, which is the reaction product of neopentylglycol, trimethylolpropane and hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides. The binder is produced from:

A. 10 to 90 wt.% polyester, hydroxyl numbers from 80 to 300 mg KOH/g 30 solid resin, acid numbers from 5 to 30 mg KOH/g solid resin and stoichiometrically calculated molar masses from 500 to 15000, consisting of reaction products

a.1) 5 to 55 mol.% neopentylglycol,

a.2) 5 to 45 mol.% trimethylolpropane,

a.3) 38 to 52 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, whereby the said mol. % in a.1), a.2) and a.3 are replenished to 100 mol.% at a certain time, and

B. 10 to 90 wt.% of acrylate resin in the specified embodiment l for component acrylate resin B.

Embodiment III for component polyester A

In a further, special embodiment of the invention, the binder contains one polyester component A in embodiment III, which is a reaction product of neopentylglycol, trimethylolpropane, hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, phthalic acid and/or its anhydride.

Embodiment III for the polyester component A in the binder is explained by the following data. Binders based on polyester-acrylate are produced from

A. 10 to 90 wt.% of polyesters with hydroxyl numbers from 70 to 300 mg KOH/g solid resin, acid numbers from 5 to 30 mg KOH/g solid resin and stoichiometrically calculated molar masses from 500 to 5000, obtained from the reaction products

a.1) 5 to 55 mol.% neopentylglycol

a.2) 5 to 45 mol.% trimethylolpropane,

a.3) 20 to 52 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its/their anhydrides, a.4) 0.5 to 32 mol.% of phthalic acid and/or its anhydride, whereby the mol % in a.1), a.2) a.3) and a.4) in particular

time replenished to 100 mol.%, and

B. 90 wt.% of acrylate resin in the above-mentioned embodiment l component of polyester acrylate B.

A further embodiment of the binder contains polyester component A in embodiment III according to the following data.

Binder based on polyester-acrylate, obtained from

A. 10 to 90 wt.% polyesters with hydroxyl numbers from 70 to 280 mg KOH/g solid resin, acid numbers from 6 to 28 mg KOH/g solid resin and stoichiometrically calculated molar masses from 500 to 12,000 made from reaction products

a.1) 8 to 50 mol.% neopentylglycol,

a.2) 5 to 44 mol% trimethylolpropane,

a.3) 25 to 51 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, a.4) 1 to 30 mol.% of phthalic acid and/or its anhydride, whereby the mol % in a.1 ), a.2) a.3) i

a.4) at a certain time replenish to 100 mol.%, i

B. 10 to 90 mol.% of acrylate resin in the already mentioned embodiment of component 1 acrylate resin B.

The binder based on polyester-acrylate, which contains one component of polyester A in embodiment III, is obtained from:

A. 10 to 90 wt.% of polyesters with hydroxyl numbers from 70 to 270 mg KOH/g solid resin, acid numbers from 7 to 26 mg KOH/G solid resin and stoichiometrically calculated molar masses from 500 to 10,000, which is produced from the reaction products

a.1) 9 to 48 mol.% neopentylglycol,

a.2) 5 to 43 mol.% trimethylolpropane,

a.3) 30 to 49 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides,

a.4) 1 to 25 mol.% of phthalic acid and/or its anhydride, whereby the mol % in a.1), a.2), a.3) and a.4) are replenished to 100 at a certain time mol.%, i

B 10 to 90% by weight of acrylate resin in the already mentioned embodiment of component acrylate resin B.

A further binder based on polyester-acrylate, which contains polyester component A in embodiment III, is produced from:

And 10 to 90 wt. % of polyesters with hydroxyl numbers from 70 to 260 mg KOH/g solid resin, acid numbers from 8 to 25 mg KOH/g solid resin and stoichiometrically calculated molar masses from 580 to 8000, produced from reaction products

a.1) 10 to 47 mol.% neopentylglycol,

a.2) 5 to 42 mol.% trimethylolpropane,

a.3) 32 to 50 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides

a.4) 1 to 20 mol.% of phthalic acid and/or its anhydride, whereby the mol % in a.1), a.2), a.3) and a.4) are topped up to 100 mol. %, i

B 10 to 90 wt.% of acrylate resin in the already mentioned embodiment l component of acrylate resin B.

Binder based on polyester-acrylate, containing polyester component A in embodiment III, produced from:

And 10 to 90 wt. % polyester of hydroxyl numbers from 70 to 255 mg KOH/g solid resin, acid numbers from 9 to 24 mg KOH/g solid resin and stoichiometrically calculated molar masses from 600 to 7000, produced from reaction products

a.1) 12 to 46 mol.% neopentylglycol,

a.2) 5 to 40 mol.% trimethylolpropane,

a.3) 35 to 59 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides

a.4) 2 to 15 mol.% of phthalic acid and/or its anhydride, whereby the mol % in a.1), a.2), a.3) and a.4) are replenished to 100 mol. %, i

B 10 to 90 wt.% of acrylate resin in the already mentioned embodiment l component of acrylate resin B.

Embodiment IV for polyester component A

In a further, special embodiment of the subject invention, the binder contains one polyester component A, in embodiment V, which is the reaction product of neopentylglycol, trimethylolpropane, hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its anhydrides, phthalic acid and/or its anhydride and possibly ingredients a.5), a.6) a.7) a.8). Embodiment IV for polyester component A is explained by the following data.

A. 10 to 90 wt.% polyesters of hydroxyl numbers of 80 to 300 mg KOH/g solid resin, acid numbers of 5 to 30 mg KOH/g solid resin and stoichiometrically calculated molar masses of 500 to 15,000, which is produced from the reaction products

a.1) 5 to 50 mol.% neopentylglycol,

a.2) 5 to 45 mol.% trimethylolpropane,

a.3) 10 to 51.5 mol.% hexahydrophthalic acid and/or hexahydrophthalic acid or its/their anhydrides

a.4) 0.5 to 32 mol.% phthalic acid and/or its anhydrides,

a.5) 0 to 18 mol.% of other alkanediols from the group of 1,2-, 1,3-, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol , neopentyl ester of hydroxypivalic acid, cyclohexanediol, trimethylpentanediol, ethylbutylpropanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, hexylene glycol, individually or in a mixture,

a.6) 0 to 18 mol.% of other dicarboxylic acids and/or hydroxydicarboxylic acids and/or its anhydride and/or from the group of 5-hydroxyisophthalic acid, isophthalic acid, terephthalic acid, halogen acids such as tetrachlor or tetrabromophthalic acid, tetrahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tricyclo decane dicarboxylic acid, endoethylenehexahydrophthalic acid, camphoric acid (1,2,2,

-trimethylcyclopentane-1,3-dicarboxylic acid), adipic acid, succinic acid, azealic acid, sebacic acid, glutaric acid individually or in a mixture.

a.7) 0-16 mol.% of monocarboxylic acids and/or hydrocarbon acids from the group of benzoic acid, p,tert.-benzoic acid, lauric acid, isonone acid, 2,2-dimethylpropionic acid, 2-ethylhexanoic acid, caproic acid , caprylic acids, capric acids, versatile acids, hexahydrobenzoic acids, hydroxypivalic acids, 3-,4-hydroxybenzoic acids, 2-hydroxyisobutyric acids, 2-,3-,4-,2,- hydroxy-3-,4-, 3 -,4-methoxybenzoic acid, 2-,3-hydroxyl-4-,4-methylbenzoic acid, 2-,3-,4-hydro phenyl acetic acid, 2-hydroxy-2-phenylpropionic acid, 3-(3-, 4-hydroxyphenylpropionic acid, individually or in a mixture,

a.8) 0 to 14 mol.% of aliphatic and/or cycloaliphatic monoalcohols with 4 to 18 atoms, individually or in a mixture, whereby the mol. % listed in a.1), a.2), a.3) a.4) and possibly in a.5), a.6), a.7) and a.8) are replenished at a certain time to 100 mol .%,

B 10 to 90 wt. % of acrylate resin according to embodiment 1 for component acrylate resin B.

Version V for polyester component A

In a further, special embodiment of the subject invention, the binder contains one polyester component A in embodiment V, which is the reaction product of neopentylglycol, trimethylolpropane, hexahydrophthalic acid and/or its anhydride, and isophthalic acid. The embodiment V for the polyester component A is explained by the following data.

A. 10 to 90 wt.% polyester, hydroxyl numbers from 80 to 300 mg KOH/g solid resin, acid numbers from 5 to 30 mg KOH/g solid resin and stoichiometrically calculated molar masses from 500 to 15,000, which is produced from reaction products

a.1) 5 to 50 mol.% neopentylglycol,

a.2) 5 to 45 mol.% trimethylolpropane,

a.3) 20 to 51.5 mol.% hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides a.6) 0.5 to 32 mol.% iso-phthalic acid, whereby the mol. %, specified in a.1), a.2) and a.6), must be supplemented to 100 mol.%.

B. 90 to 10 wt.% of acrylate resin in the already mentioned embodiment of component 1, acrylate resin B.

Embodiment VI for polyester component A

In a further, special embodiment of the invention, the binder contains one polyester component A in embodiment VI, which is the reaction product of other alkanediols a. 5) trimethylolpropane, hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its/their anhydrides and phthalic acid and /or its anhydride. One embodiment VI for the polyester component A is explained by the following data.

Embodiment VI is also clarified in Table IV, Experiments 6.2 to 6.4.

Binder based on polyester-acrylate is produced from

A. 10 to 90 wt.% polyester obtained from reaction products

a.2) 18 to 45 mol.% trimethylolpropane,

a.3) 35 to 52 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides

a.4) 1.5 to 10 mol.% phthalic acid,

a.5) 3 to 35 mol.% of other alkanediols from the group of 1,2-, 1,3-, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, neopentyl ester of hydroxypivalic acid, cyclohexanediol, trimethylpentanediol, ethylbutylpropanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, hexylene glycol individually or in a mixture, whereby the components listed in a.1), a.2), a.3 ), a.4) and a.5), must be supplemented to 100 mol.%.

B 90 to 10 wt.% of acrylate resin in the already mentioned embodiment l component acrylate resin B.

The polyesters essential to the present invention as polyester component A are obtained in a known manner by methods, which are for example described in detail in "Ullmans Encvclopadie der technischen Chemie", published by Chemie Weinheim, 4th edition (1980), volume 19, pages 61 ff , or in "Lackungsharze", author H. Wagner and H.F Sarx, publisher Čari Hansen, and Munchen (1971), pages 86 to 152. Esterification in this case takes place in the presence of catalytic amounts of a common esterification catalyst, such as an acid, alkali or compounds with transition metals, such as titanium tetrabutylate, at approximately 80 to 260°C, especially at 100 to 230°C. Esterification is carried out until the desired values of hydroxyl and acid numbers are reached. Esterification without the use of a catalyst is preferred. The molecular weight of the polyester component A can be stoichiometrically calculated from the starting raw materials (taking into account the achieved hydroxyl and acid numbers).

The production of binders based on polyester-acrylate is carried out by polymerization of monomers that are a component of acrylate B, in the presence of an inert solvent and polyester component A. It is preferable to use very small amounts of an organic, inert solvent with a high boiling point (at least 120°C), which is loaded together with polyester into the esterification reactor. This mixture is heated to the boiling temperature, approximately between 120 and 210°C, and then monomers for polymerization are continuously added, together with the initiator, or the initiator mixture, for 2 to 12 hours. After the completion of the monomer addition, the polymerization is continued for another 2 to 6 hours in the same temperature range. The reaction product is precipitated with a solids content of 60 to 100 wt.%. A solids content of 70 to 95 wt.% is preferred. Then the viscosity of the reaction product with an organic solvent, suitable for the intended purpose, is adjusted to good processability, e.g. to max. 20000 mPa-s at 23° C.

For the production of the binder of the subject invention, the usual compounds that generate radicals or their mixtures come into consideration as polymerization initiators. These are, for example, aliphatic azo compounds, diacylperoxides, peroxydicarbonates, alkylperesters, alkylhydroperoxides, perketals, dialkylperoxides or ketone peroxides. It is preferred to use dialkyl peroxides such as di-t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, dibenzoylperoxide or di-t-amylperoxide and alkylperesters such as t-butylperoxy-2-ethylhexanoate, 1,1-di- (t -amylperoxy)cyclohexane, 1,1-di-(tert.-butylperoxy)cyclohexane, t-amylperoxyacetate, ethyl-3,3-di-(t-amylperoxy)butyrate, di-t-amylperoxide, 3-ethylpent-3- yl-peroxy-2-ethylhexanoate and di-(3-ethyl-pent-3-yl)-peroxide. Furthermore, 2,5-dimethyl-2,5-di-(tert.-butylperoxy)hexane-(3), tert.-butylperoxybenzoate, tert. -butylperoxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5-di(benzoylperoxy)-hexane, 0-tert.-butyl-0-2-(ethylhexyl)-monoperoxycarbonate, 2,5-dimethyl -2,5-di-(tert.-butylperoxy)-hexane, dicumylperoxide, tert.-butylhydroperoxide, tert.-amylhydroperoxide, cumylhydroperoxide, 2,5-dimethyl-2,5-dihydroperoxyhexane, diisopropylbenzene- monohydroperoxide and 2, 2-azo-di(2-acetoxypropane).

The proportion of initiator can be, for example, 1 to 8 wt.%, better up to 6, and best up to 5 wt.%, in relation to the total mass of the starting components. Suitable polymerization mixtures consist, for example, of di-tert.-butylperoxide and dibenzoylperoxide, tert.-butylper-2-ethylhexanoate and 1,1-di-tert.-amylperoxide, tert.-butylper-2-ethylhexanoate and di- of tert.-butylperoxide, butylper-2-ethylhexanoate and 1,1-di(tert.-butylperoxycyclohexane, tert.-butylper-2-ethylhexanoate and dibenzoyl peroxide. However, other mixtures are also usable.

Chain transfer agents such as mercaptans, thioglycolic acid esters, chlorinated hydrocarbons, especially dodecylmercapten and mercaptoethanol can be used to regulate the molecular weight.

For polymerisation in the solvent, inert solvents common in the varnish industry can be used, individually or in a mixture, with a boiling point of 80 to 220°C, especially a boiling point of 125 to 185°C. Preference is given to those organic solvents that are later used in finished coating products. Examples of these solvents are: glycol ethers, such as ethylene glycol dimethyl ether, glycol ether ester; esters such as butylglycoacetate, 3-methoxy-n-butylacetate, butyldiglycoacetate, methoxypropylacetate, ethoxypropylacetate, butylacetate, ethyl-3-ethoxypropionate, isobutylacetate, amylacetate; ketones such as methyl-n-amyl ketone, methyethyl ketone, methylisobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone; aromatic hydrocarbons such as xylene. Shellsol A (registered trademark for a mixture of aromatic hydrocarbons) and aliphatic hydrocarbons can also be used in a mixture with the aforementioned solvents. The binder, obtained by polymerization in a solvent, can be diluted with other inert organic solvents common in the varnish industry, suitable for the intended use.

Polyester as the primary product for component A is obtained by polycondensation at approximately 170°C to 230°C. The absence of solvents and catalysts is preferred. Polycondensation takes place over approximately 6 to approximately 15 hours. The solvent-free polycondensation product is a highly viscous, sticky or solid mass that, depending on its composition, has different viscosities, hydroxyl and acid numbers. The value of acid numbers ranges between 5 and 30 mg KOH/g solid resin. The value of hydroxyl numbers ranges from 70 to 300 mgKOH/1g of solid resin. Calculated molecular weights are 400 to 15,000.

Production of polyester component A, which is the primary product in the production of binders based on polyester-acrylate.

Polyester 1 for embodiment I of polyester component A

In order to carry out the polycondensation process, 4168 g of neopentylglycol and 4626 g of hexahydrophthalic anhydride are transferred to the reactor and heated to 180°C with nitrogen flow and a mounted column, due to the separation of water. After that, the temperature continuously rises to 220°C. The polycondensation is completed after 8 to 13 hours, when an acid number of 17 to 20 is reached. The utilization is about 95.5%.

This polyester 1 was obtained from 57.143 mol.% neopentylglycol and 42.857 mol.% hexahydrophthalic anhydride.

The resulting polyester 1, after dissolving in butyl acetate, at a concentration of 80 wt.%, at 20°C will have a viscosity of 1800 to 4000 mPas at 20°C.

The following polyesters for Embodiment I are listed in Table I

Table I: polyesters 1.1 -1.6 for embodiment I

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Polyester 2 for embodiment II

Polyester from

3.0 moles of neopentyl glycol 312 g

3.8 moles of trimethylolpropane 509 g

6.0 moles of hexahydrophthalic anhydride 925 g

Average molecular weight around 1330

This mixture is heated in a nitrogen atmosphere to 190 to 200°C. The water produced by the reaction is continuously drained. During 7 to 12 hours, the temperature is constantly raised to 220°C until the acid number drops to a value of 15 to 25. After cooling, the reaction product is in solid form. After repeating the reaction multiple times, the following values were found in polyesters:

1st attempt 2nd attempt

hydroxyl numbers (DIN 53240) 196 200

acid numbers (DIN 53402) 18.7 19

of viscosity (DIN 3019) in mPa.s 2560 2880

Polyester consists of 53 mol.% polyol and 47 mol.% dicarboxylic acid.

Polyester 3 for embodiment II

Polyester from

3.0 moles of neopentyl glycol 312 g

3.4 moles of trimethylolpropane 456 g

6.0 moles of hexahydrophthalic anhydride 925 g

Average molecular weight around 2330

This mixture is heated in a nitrogen atmosphere to 190 to 200°. The water produced by the reaction is continuously drained. During 3 to 10 hours, the temperature is constantly raised to 235°C until the acid number drops to a value of 15 to 25. After cooling, the reaction product is in solid form. After repeating the reaction multiple times, the following values were found in polyesters:

1st attempt 2nd attempt

hydroxyl numbers (DIN 53240) 156 158

acid numbers (DIN 53402) 20.2 18.6

viscosity (DIN 3019) in mPa.s 3120 4480

Polyester consists of 51.6 mol.% polyol and 48.4 mol.% dicarboxylic acid

Polyester 4 for embodiment II

Polyester from

0.2 moles of neopentyl glycol 20.84 g

1.62 moles of trimethylolpropane 218.746 g

1.8 moles of hexahydrophthalic acid anhydride 277.56 g

Average molecular weight around 2900

This mixture is heated in a nitrogen atmosphere to 190 to 205°C. The water produced by the reaction is continuously drained. During 4 to 10 hours, the temperature is constantly raised to 230°C until the acid number drops to a value of 10 to 20. After cooling, the reaction product is in solid form. The following values were found in polyester:

hydroxyl number (DIN 53240) 210

acid number (DIN 53402) 15.9

viscosity (DIN 3019) in mPa.s 5500

Polyester consists of 50.414 mol.% polyol and 49.587 mol.% dicarboxylic acid.

The viscosity, specified for polyesters 2,3 and 4 (measured according to DIN 53019) at 23°C in mPa.s refers to their 70 wt.% solutions in butyl acetate. The following polyesters for embodiment II are listed in Table II:

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Polyester 5 for embodiment III

Polyester from

2.5 moles of neopentyl glycol 260.55 g

1.5 moles of trimethylol propane 201.3 g

3.0 moles of hexahydrophthalic anhydride 462.6 g

This mixture is heated in a nitrogen atmosphere to 190 to 220°C. The water produced by the reaction is continuously drained. During 5 to 10 hours, the temperature is constantly raised to 220°C until the acid number drops to a value of 15 to 25.

After cooling to 160°C, 0.25 mol, 37.025 g of phthalic anhydride are added and heated to 190 to 220°C in a nitrogen atmosphere. The water produced by the reaction is constantly drained away. The temperature is continuously raised to 220°C for 1 to 5 hours, until the acid number drops to 10 to 25. After cooling, the reaction product is in solid form. By adding 380 g of butyl acetate, the product is diluted, so that the non-volatile content is about 70 wt.%. The following values were found in polyesters by multiple repetitions of the reaction:

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Polyester consists of 55.17 mol.% and 44.83 mol.% dicarboxylic acid. The following polyesters for embodiment III are listed in Table III:

Table III: polyesters 5.1-5.2 for embodiment III

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Polyesters for embodiments IV and VI are listed in Table IV:

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The following polyesters for embodiment V are listed in Table V:

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As component b.1), hydroxyalkyl (meth)acrylates with 2 to 5 C atoms in the hydroxyalkyl residue are suitable, namely hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and hydroxyamyl (meth)acrylate individually or in mixtures .

Aromatic vinyl compounds of styrene (alkylphenylethene), eg α-methylstyrene, α-chlorostyrene and various vinyltoluenes, are suitable as component b.2).

Alkyl(meth)acrylates with 1 to 9 C atoms in the alkyl residue can be used as component b.3) such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl (meth)acrylate, tert-butyl(meth)acrylate, amyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl(meth) acrylate individually or in a mixture.

Example l

Production of binder according to embodiment I of polyester component A

In a polymerization reactor with a dropping funnel, a mixer and a cooler with a water separator, was placed

2100 g of polyester l as polyester component A i

525 g of ethoxypropyl acetate

and heated to 194°C. During 7 hours, at the same temperature, monomer and initiator mixtures were added evenly

700 g of 2-hydroxypropyl methacrylate,

3060 g of styrene,

140 g of acrylic acid,

1000 gisobutylmethylacrylate,

280 g of tert.-butylperoxy-2-ethylhexanoate.

After the addition was completed, the polymerization continued at the same temperature for 3 hours.

The resulting binder, expressed on a solids basis, has an acid number of 15.3 mg KOH/g of solid resin and a calculated hydroxyl number of 85 mg KOH/g of solid resin. The solid content is 93 wt.%.

After diluting the binder with 2475 g of butyl acetate, the following characteristics were obtained: solids content 69.8 wt.%, according to DIN 53216 viscosity 1200 mPa.s at 23°C, according to DIN 53019.

Example 2

Production of binder according to embodiment I of polyester component A

In a polymerization reactor with a dropping funnel, a mixer and a cooler with a water separator,

2100 g of polyester 1 as polyester component A

525 g of ethoxypropyl acetate

and heated to 197° C. During 7 hours, at the same temperature, a mixture of monomers and initiators, consisting of

700 g of 2-hydroxyethyl methacrylate,

700 g of 2-hydroxypropyl methacrylate

2660 g of styrene,

140 g of acrylic acid,

700 g of isobutyl methacrylate,

280 g of tert.-butylperoxy-2-ethylhexanoate.

After the addition was completed, the polymerization continued for 3 hours. The resulting binder, expressed on a solids basis, has an acid number of 15.5 mg KOH/g of solid resin and a calculated hydroxyl number of 127 mg KOH/g of solid resin. The solid content is 93 wt.%.

After diluting the binder with 2475 g of butyl acetate, the following characteristics were obtained:

solids content 69.5 wt.%, according to DIN 53216

viscosity 1200 mPa.s at 23° C, according to DIN 53019

Further binders for embodiment I of polyester component A are listed in Table VI

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Further binders for embodiment II of polyester component A are listed in Table VII:

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Further binders for embodiment form III of polyester component A are listed in Table VIII:

Table VIII: production of binders 4.1 to 4.19 in embodiment III of polyester A

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Described polyesters 1, from 1.1 to 1.6 for embodiment I, polyesters 2, 3, 4, 4.1 to 4.5 for embodiment II, polyesters 5, from 5.1 to 5.9 for embodiment III, polyesters 6.1 to 6.2 for embodiment IV, polyester 7 as embodiment V and polyesters 6.3 and 6.4 as embodiment VI, can be combined as polyester component A with monomers for the production of binders. They can also be combined with acrylate resin B, according to examples 1 and 2, experiments 2.1 to 2.8, experiments 3.1 to 3.14 and experiments 4.1 to 4.9. Thus, binders can contain 10 to 90 wt. % polyester A and 10 to 90 % acrylate resin B. Special tests have shown that these binders, by cross-linking with di- and/or polyisocyanates, also provide coatings with valuable properties.

When using binders suitable for the subject invention, they can possibly be mixed with other organic polyhydroxyl compounds known from polyurethane varnish technology, as a polyhydroxyl component.

These other polyhydroxyl compounds can be common polyester, polyether or polyacrylate polyols.

Further, suitable polyhydroxyl compounds, if they come to be used at all with the binders from the subject invention, are already known, technically modern Spoliacrylate-polyols. Suitable polyacrylate polyols for mixing are, for example, varnish solvents such as the type of soluble copolymers already mentioned in the examples, which can be obtained under the names E-OS 40 01 580, DE-OS 41 24 167 or DE-OS 28 58 096. The content of hydroxyl groups in these polyacrylate polyols is usually between 2 and 5 wt.%. In use, the binders of the present invention can be mixed with up to 90, especially up to 50 hydroxyl-equivalent %, in relation to all polyhydroxyl compounds in other polyols, mentioned as an example. However, special preference is given to the binders of the present invention as the only polyol components when used according to the invention.

Polyisocyanates, typical for varnishes, can be used for cross-linking the binder from the present invention. The proportion of polyisocyanate crosslinker is chosen so that there are 0.5 to 1.5 isocyanate groups per hydroxyl group of the binder mixture. Excess isocyanate groups can be removed by their reaction with moisture and thus contribute to the crosslinking process. Aliphatic, cycloaliphatic and aromatic polyisocyanates can be used such as hexamethylene diisocyanates, trimethylhexa methyl diisocyanates, isophorone diisocyanates, 4,4-diisocyanatodicyclohexylmethane, toluylene-2,4-diisocyanate, o-m- and p-xylyl diisocyanate, 4,4'diisocyanatodiphenylmethane; polyisocyanate derivatives with CH-, NH-, or OH-acidic groups; likewise, for example, polyisocyanates containing biuret, allophanate, urethane or isocyanurate groups. An example of such polyisocyanates is the reaction product with biurethnium groups, obtained from 3 moles of hexamethylenediisocyanate and 1 mole of water, with an NCO- content of about 22% (corresponds to the commercial product with the trademark Desmodur N BAYER AG); one polyisocyanate with an isocyanate group obtained by trimerization of 3 moles of hexamethylene diisocyanate with an NCO content of about 21.5% (corresponds to the commercial product with the trademark Desmodur N 3390 BAYER AG) or polyisocyanates with urethane groups, which are reaction products of 3 moles of toluene diisocyanate and 1 mole of trimethylpropane, with an NCO content of about 17.5% (corresponds to the commercial product with the trademark Desmodur L 3390) The products with the trademark Desmodur N and Desmodur N 3390, BAYER AG, are primarily used. For uses suitable for the invention, two-component polyurethane varnishes contain a binder and polyisocyanate component in an equivalent ratio of isocyanal and hydroxyl groups from 2:1 to 1:2, especially 1.5:1 to 1:1.5. The two-component binders obtained by mixing both components have a limited processing time of about 2 to 48 hours. are used with the usual auxiliaries and additives. These auxiliaries and additives can be added either in a mixture or individually not the components, before their mixing.

As auxiliaries and additives, for example inert solvents such as ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethoxypropyl acetate, methoxypropyl acetate, ethyl-3-ethoxypropionate, 3-methoxy-n-butyl acetate, butyl glycol acetate, toluene, xylene, petroleum test gasoline, test gasoline, or any mixture of these solvents. Solvents are used in amounts up to 75, especially up to 70 wt.% in relation to the total amount of the mixture.

Further, possibly used auxiliaries and additives are, for example, softeners such as tricresyl phosphate or phthalic acid diester, chlorparafm; pigments and fillers such as titanium oxide, barium sulfate, chalk, carbon black; catalysts such as N,N-dimethylbenzylamine, N-methylmorpholine, lead octoate or dibutyl cositrenyl laurate; funds for improved spillages; thickeners, possibly stabilizers such as substituted phenols and silanes with organic functional groups as adhesion agents; light-protecting agents, for example sterically hindered amines which are also described in DE-OS 2 417 353 (=US-PS 4 123 418 and US-PS 4 110 304) and DE-OS 2 456 864 (=US-PS 3 993 655 and US-PS 4,221,701). Particular preference is given to the compounds: bis(1,2,2,2,6,6-pentamethylpiperidyl-4)-sebacate, bis-(2,2,6,6-tetramethylpiperidyl-4)-sebacate, bis-(1, 2,2,6,6,-pentamethyl piperidyl-4) ester of n - butyl - (3,5-di-tert.-butyl -4-hydroxybenzyl) malonic acid.

Moisture attached to fillers and pigments can be removed by previous drying or mixing with hygroscopic substances, such as zeolite molecular sieves.

Drying of varnish films, obtained by using the subject invention, can take place at room temperature. It is not necessary to increase the temperature to achieve the optimal properties mentioned at the beginning. Relatively fast drying at room temperature can be additionally accelerated by heating the space to approximately 60 to 120°C, preferably 60 to 80°C, for 20 to 40 minutes. It is possible to shorten the baking process with a higher drying temperature, but it is not recommended in the presence of many substrates, such as pieces of plastic.

The reactive varnishes of the subject invention are suitable above all for varnishing metals as well as plastics, but also for other substrates. The reactive varnishes of the present invention can be applied to substrates by conventional methods in varnish technology, such as coating, spraying or dipping. The reactive varnishes of the present invention are equally suitable for the production of base coats, intermediate coats and top coats on the surfaces to be varnished.

Example 5

Production of base coating and/or filler based on 70% binder solution from example 1u

ethoxypropylacetate/butylacetate (5:25)

Mass fractions

Binder as in example 1 1900

Siliconol LO 50, 1% solution in xylene 100

KronosTitandioxide 2160 1500

Eisenoxidgelb 1500

Talk AT extra 800

Zinc phosphate ZP 10 1000

Aerosil 200 500

Wolllast 400 ST 2300

Bentone + Bykumen 200

Butylacetate______________________________________ 2000

Total_____________________________________ 10000

20 min, in a disperser with water cooling

Viscosity, 20° C in a beaker with a spout of 4 mm______________________ 26 sec

Desmodur N 75 5 5

ThinnerBd 1316_________________________________ 1.5

Usability time, currently 21 sec.

+ 1 hour 22 seconds.

+ 2 hours 26 seconds.

+ 2.5 hours 29 seconds.

+ 3 hours 32 seconds.

+ 4 hours 45 seconds.

+ 5 hours_______________________________________________ 65 sec.

Dry to sand 14 min.

T2 16 min.

T3 20 min.

T4 30 min.

T5 65 min.

T6 33 min

T7_______________________________________________ 100 min.

Solids content after 21 sec. l.5g/1 hour, at 125°C + 2 ml Eac/DIN 53216= 70.80 wt.%.

The advantage of the filler, which is made with the binder from the present invention, is a higher content of solids. A comparison with good commercial products of the same purpose shows that its solids content is 10 to 20 wt. % higher, at the dispersion viscosity, and therefore undoubtedly has more favorable properties in terms of protecting the environment. It achieves dryness against sand and dust already after 14 minutes.

Furthermore, table IX lists examples of usable 2-component topcoats based on the binder from the subject invention

Table IX: production of white lacquer

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Based on the results of the previously mentioned examples of varnishes in Table IX, the non-volatile fraction is, compared to the usual varnish systems, 10 to 20% higher and thus undoubtedly less harmful to the environment.

Furthermore, Table X lists examples of usable 2-component varnishes for furniture based on the binder of the present invention: comparative experiments with white reactive varnishes for wood using the binder of the present invention 2.1 and a good, commercial acrylate copolymer named Syntalat® A-1613, as 51% solution in xylene/methylisobutylketone (1:1) for the same purpose.

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The results of comparative tests with white two-component varnishes for wood in Table X show that the two-component varnish, based on binder 2.1, is a true "high solid" varnish, because the non-volatile fraction is 56.2 wt.%. With the commercial Syntalat A-1613, only 39.0 wt.% of non-volatile substances was achieved. Furthermore, it is worth mentioning that the gloss of the covering film is undoubtedly improved when using the binder from the subject invention. Other properties, such as resistance to ethanol or dryness, have retained their undiminished value.

The surprisingly good compatibility of binder 2.1 with fast-drying reagents such as Desmodur HL and CAB, which are used as additives in varnishes for varnishing furniture.

Furthermore, table XI lists comparative examples of reactivity and compatibility of two-component clear (pigment-free) varnishes based on the binder from the subject invention, in the field of wood varnishing: application of the binder 4.7. of the subject invention. A comparable binder is a good, commercial acrylate copolymer for the same purpose, called Syntalat® A-075 55, as a 55% solution in xylyl/butylacetate (1:4).

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The data in Table XI show a surprisingly very good compatibility of binder 4.7 with quick-drying reagents, such as Desmodur HL and CAB, which are used as additives in the production of furniture lacquers. In addition, binder 4.7 achieves very fast initial drying, 103 seconds, after 1 day, and the final hardness of the lacquer film after only 2 days. Therefore, furniture coated with this binder can be stored faster, which is an unusually large cost and time saving compared to commercial binders.

Character interpreter:

Thinner Bd 1316 = EPA = Ethoxypropylacetate 25

Buac = Butylacetate 25

SSA = Shellsol A 20

Xylol 25

Butoxyl 5

EEP = ethyl-3-ethoxypropionate,

CH50AL= 1.1.di(tert.-butylperoxy)cyclohexane,

BP75W= dibenzoyl peroxide,

DTBP= di.tert.-butyl peroxide,

TBPEH= tert.-butylper-2-ethylhexanoate,

DTAP= tert.-amyl peroxide.

CAB= cellulose acetobutyrate.

Claims (25)

1. Binder based on polyester-acrylate, indicated by the fact that it is made of: And 10 to 90 wt. % of polyester from a.1) 0 to 63 mol. % of neopentylglycol, a.2) 0 to 45 mol. % of trimethylol propane a.3) 10 to 52 mol. % of hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its anhydrides, a.4) 0 to 32 mol. % of phthalic acid and/or its anhydride, a.5) 0 to 35 mol. % of other alkanediols from the group of 1,2-, 1,3-, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, neopentyl ester of hydroxypivalic acid, cyclohexanediol, trimethylpentanediol, ethylbutylpropanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, hexylene glycol, individually or in a mixture, a.6) 0 to 32 mol. % of other dicarboxylic acids and/or hydroxydicarboxylic acids and/or their anhydrides and/or from the group of 5-hydroxyisophthalic acid, isophthalic acid, terephthalic acid, halogen acids such as tetrachlor or tetrabromophthalic acid, tetrahydrophthalic acid,! ,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tricyclodecane-dicarboxylic acid, endoethylenehexahydrophthalic acid, camphoric acid (1,2,2-trimethylcyclopentane-1,3-dicarboxylic acid), adipic acid, succinic acid, azelaic acid , sebacic acids, glutaric acids individually or in a mixture, a.7) 0 to 16 mol. % of monocarboxylic acids and/or hydroxycarboxylic acids from the group of benzoic acid, p.tert.-butylbenzoic acid, lauric acid, isonone acid, 2,2-dimethylpropionic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, versatile acid, hexahydrobenzoic acid, hydroxypivalic acid, 3-,4-hydroxybenzoic acid, 2-hydroxyisobutyric acid, 2-,3,-4,-2,-hydroxy-3,4-3-,4-methoxybenzoic acid, 2- ,3-hydroxy-4-,4-methoxybenzoic acid, 2-,3-,4-hydrophenylacetic acid, 2-hydroxy-2-phenylpropionic acid, 3-(3-,4-hydroxyphenylpropionic acid individually or in a mixture, a.8) 0 to 14 mol. % of aliphatic and/or cycloaliphatic monoalcohols with 4-18 C atoms, individually or in a mixture. whereby the mol. The percentages, listed under a.1), a.3) and possibly a.2), a,4), a.5) a.6), a.7) and a.8) are added to 100 mol. %-like, B 90 to 10 wt.% of acrylate resin from b.1) 5 to 55 wt.% of hydroxyalkyl(meth)acrylate with 2 to 5 C-atoms in the hydroxylalkyl residue, individually or in a mixture, b.2) 0 to 80% by weight of aromatic vinyl compounds, individually or in a mixture, b.3) 0 to 95% by weight of alkyl(meth)acrylates with 1 to 9 carbon atoms in the alkyl residue, individually or in a mixture, b.4) 0.0 to 6 wt.% of (meth)acrylic acid, individually or in a mixture, whereby b.1) and possibly b.2), b.3 and/or b.4 possibly complement up to 100 wt. %-like. 2. Binder based on polyester-acrylate according to claim 1, indicated by the fact that it is made of: A. 10 to 90 wt. % of polyester from a.1) 5 to 90 mol.% of such neopentylglycol, a.2) 0 to 45% by weight of trimethylpropane, a.3) 15 to 52 mal.a% of hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its anhydrides, a.4) 0 to 32 mol.% of phthalic acid and/or its anhydride, a.5) 0 to 18 mol. other alkanediols from the group of 1,2-, 1,3-, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, neopentyl ester of hydroxypivalic acid, cyclohexanediol, trimethylpentanediol, ethylbutylpropanediol , ethylene glycol, diethylene glycol, triethylene glycol, 1,-2-propylene glycol, dipropylene glycol, hexylene glycol, individually or in a mixture, a.6) 0 to 32 mol.% of other dicarboxylic acids and/or hydroxydicarboxylic acids and/or their anhydrides and/or from the group of 5-hydroxyisophthalic acid, isophthalic acid, terephthalic acid, halogen acids, such as tetrachlor or tetrabromophthalic acid, tetrahydrophthalic acid, 1.2 -cyclohexanedicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 4-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tricyclo decandicarboxylic acid, endoethylenehexahydrophthalic acid, camphoric acid (1,2,2,-trimethylcyclopentane-1,3- dicarboxylic acid), adipic acid, succinic acid, azelaic acid, sebacic acid, glutaric acid, individually or in a mixture. a.7) 0 to 16 mol.% of monocarboxylic acids and/or hydroxycarboxylic acids from the group of benzoic acid, p.tert.-butylbenzoic acid, lauric acid, isonanoic acid, 2,2-dimethylpropionic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, versatilic acid, hexahydrobenzoic acid, hydroxyipivalic acid, 3-,4-hydroxybenzoic acid, 2-hydroxybutyric acid, 2-,3,-4,-,2,- hydroxy-3-,4-,3 -,4,-methoxybenzoic acid, 2-,3-hydroxy-4-,4-methylbenzoic acid, 2-,3-,4-hydrophenylacetic acid, 2-hydroxy-2-phenylpropionic acid, 3-(3-,4 -)-hydroxyphenylpropionic acid, individually or in a mixture, a.8) 0 to 14 mol. % of aliphatic and/or cycloaliphatic monoalcohols with 4 to 18 C atoms, individually or in a mixture, whereby the mol. The percentages specified in a.l), a.3) and possibly in a.2), a.4), a.5), a.6), a.7) and a.8) are replenished at a certain time on 100 mol.%, and B 90 to 10% by weight of acrylate resin according to requirement 1, part B. 3. Binder based on polyester-acrylate according to claim 2, characterized by the fact that it is made of: And 10 to 90 wt.% of polyesters with stoichiometrically calculated molecular masses from 400 to 1300, acid numbers from 5 to 30 mg KOH/g solid resin and hydroxyl numbers from 70 to 270 mg KOH/g solid resin from a.1) 53 to 63 mol.% neopentylglycol, a.3) 37 to 47 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its/their anhydrides, whereby a.1) and a.3) are supplemented up to 100 wt.% and B 10 to 90 wt.% acrylate resin according to requirement 1, part B. 4. Binder based on polyester acrylate according to claim 2, characterized in that it is made of A. 10 to 90% by weight of polyesters with stoichiometrically calculated molecular masses between 400 and 1100, acid numbers from 10 to 25 mg KOH/g solid resin and hydroxyl numbers from 80 to 265 mg KOH/g solid resin from a.1) 54 to 62 mol.% neopentylglycol, a.3) 38 to 46 wt.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, whereby a.1) and a.3) are supplemented up to 100 wt.%, B 10 to 90 wt.% acrylate resin according to requirement 1, part B. 5. Binder based on polyester-acrylate according to claim 2, characterized in that it is made of A. 10 to 90% by mass of polyester from a.1) 55 to 60 mol.% neopentylglycol, a.3) 40 to 45 wt.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, whereby a.1) and a.3) are supplemented up to 100 wt.%, B 10 to 90 wt.% acrylate resin according to requirement 1, part B. 6. Binder based on polyester-acrylate according to claim 2, characterized in that it is made of A. 110 to 90 wt. % of polyester from a.1) 56 to 60 mol.% neopentylglycol a.3) 40 to 54 wt.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, whereby a.1) and a.3) are supplemented up to 100 wt.%, B 10 to 90 wt.% acrylate resin according to requirement 1, part B 7. Binder based on polyester-acrylate according to claim 2, characterized in that it is made of And 10 to 40 wt. % of polyester from a.1) from 54 to 62.5 wt.% of neopentylglycol a.3) from 37.5 to 46 wt.% of hexahydrophthalic acid and/or methylethylhexahydrophthalic acid or its/their anhydrides, whereby a.l) and a.3) are supplemented up to 100 wt.%, B 60 to 90 wt.% acrylate resin b.1) 5 to 35 wt.% hydroalkyl(meth)acrylate with 2 to 5 C atoms in the alkyl residue, individually or in a mixture. b.2) 30 to 80 wt.% of aromatic vinyl compounds, individually or in a mixture, b.3) 0 to 30 wt.% alkyl (meth)acrylate with 1 to 9 C atoms in the alkyl residue, individually or in a mixture, b.4) 0.0 to 6 wt. % of (meth)acrylic acid, individually or in a mixture. 8. Binder according to claim 7, characterized in that acrylate resin B contains b.3) 5 to 30 wt.% alkyl (meth)acrylate with 1 to 9 C atoms in the alkyl residue, individually or in a mixture. 9. Binder according to one of claims 7 to 8, characterized in that acrylate resin B contains b.4) 0.1 to 5 wt. % of acrylic or (meth)acrylic acid. 10. Binder according to one of claims 7 to 9, indicated by the fact that the concentration of partial component b.3) ranges from 5 to 30 wt.% in relation to acrylic acid. 11. Binder based on polyester-acrylate according to claim 2, characterized in that it is made of A. 15 to 40 wt.% of polyester from a.1) from 55 to 61.6 wt.% of neopentylglycol a.3) from 38.4 to 45 wt.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, whereby a.1) and a.3) are supplemented up to 100 wt.%, B 60 to 85 wt.% acrylate resin from b.1) 8 to 32 wt. % of hydroxyalkyl(meth)acrylate with 2 to 4 C atoms in the alkyl residue, individually or in a mixture. b.2) 40 to 75 wt.% of aromatic vinyl compounds, individually or in a mixture, b.3) 5 to 28 wt.% alkyl(meth)acrylate with 2 to 6 C atoms in the alkyl residue, individually or in a mixture, b.4) 0.1 to 4.5% by weight of (meth)acrylic acid, individually or in a mixture. 12. Binder based on polyester-acrylate according to claim 2, characterized in that it is made of A. 20 to 35 wt.% of polyester from a.1) 55 to 60 wt.% neopentylglycol a.3) 40 to 45 wt.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, whereby a.1) and a.3) are supplemented up to 100 wt.%, B 65 to 80 wt.% acrylate resin from b.1) 10 to 30 wt. % of hydroxyalkyl(meth)acrylates with 2 to 4 C atoms in the alkyl residue, individually or in a mixture. b.2) 45 to 70 wt. % of such aromatic vinyl compounds, individually or in a mixture, b.3) 10 to 25 wt.% alkyl (meth)acrylate with 2 to 5 C atoms in the alkyl residue, individually or in a mixture, b.4) 0.5 to 4.0 wt.% of (meth)acrylic acid, individually or in a mixture. 13. Binder based on polyester-acrylate according to claim 1, characterized in that it is made of. A. 10 to 90 wt.% of polyesters with hydroxyl numbers from 80 to 300 mg KOH/g solid resin and acid numbers from 5 to 30 mg KOH/g solid resin, which is made from reaction products a.1) 5 to 55 mol.% neopentylglycol, a.2) 5 to 45 mol.% trimethylpropane, a.3) 38 to 52 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides, whereby the mol % in a.1), a.2) and a.3 are topped up to 100 at certain times mol.%, i B. 10 to 90 wt.% acrylate resin according to requirement 1, part B 14. Binder based on polyester-acrylate according to claim 1, characterized in that it is made from A. 10 to 90% by weight of polyester with hydroxyl numbers from 70 to 300 mg KOH/g of solid resin, acid numbers from 5 to 30 mg KOH/g of solid resin, made from the reaction products a.1) 5 to 55 mol.% neopentylglycol a.2) 5 to 45 mol.% trimethylpropane, a.3) 20 to 52 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its/their anhydrides, a.4) 0.5 to 32 mol.% of phthalic acid and/or its anhydride, whereby the mol. %s in a.l), a.2) a.3) i a.4) replenish to 100 mol.% at a certain time, B. 90 to 100 wt. % of acrylate resin according to requirement 1, part B. 15. Binder based on polyester-acrylate according to claim 1, characterized in that it is made of A. 10 to 90 wt.% polyester obtained from reaction products a.2) 18 to 45 mol.% trimethylolpropane, a.3) 35 to 52 mol.% of hexahydrophthalic acid and/or methylhexahydrophthalic acid or its/their anhydrides a.4) 1.5 to 10 mol.% phthalic acid, and/or its anhydride a.5) 3 to 35 mol. % of other alkanediols from the group of 1,2-, 1,3-, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, neopentyl ester of hydroxypivalic acid, cyclohexanediol , trimethyl pentadiol, ethylbutylpropanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, hexylene glycol, individually or in a mixture, whereby the components listed in a.1), a.2), a.3), and .4) and a.5) must be topped up to 100 mol.% at a certain time. B 90 to 10 wt.% acrylate resin according to claim 1, part B. 16. Binder based on polyester-acrylate according to claim 1, characterized in that it is obtained from A. 10 to 90 wt. % of polyester with hydroxyl numbers from 80 to 300 mg KOH/g of solid resin, acid numbers from 5 to 30 mg KOH/g of solid resin, obtained from the reaction products a.1) 5 to 50 mol.% neopentylglycol a.2) 5 to 45 mol.% trimethylpropane, a.3) 20 to 51.5 mol.% hexahydrophthalic acid and/or methylhexahydrophthalic acid and/or its/their anhydrides, a.6) 0.5 to 32 mol.% isophthalic acid, whereby the mol. The percentages in a.1), a.2), a.3) and a.4) are supplemented at certain times at 100 mol.%, B. 10 to 90 wt. % of acrylate resin according to claim 1, part B. 17. Binder based on polyester-acrylate according to one of the requirements from 1 to 6 and from 13 to 16, indicated by the fact that in them component B has the following meaning B. 90 to 10 wt. % of acrylate resin from b.1) 9.3 to 53.6 wt. % of hydroxyalkyl(meth)acrylates (one or more) with 2 to 4 C atoms in the hydroxyalkyl residue, individually or in a mixture, b.2) 0 to 65.4 wt.% styrene, b.3) 12.2 to 90.4 wt. % of alkyl(meth)acrylate with 1 to 8 C atoms in the alkyl residue, individually or in a mixture, b.4) 0 to 5.7 wt. % of (meth)acrylic acid, individually or in a mixture, whereby the quantities specified in b.l) b.3) and possibly b.2),) and/or b.4, are supplemented up to 100 wt.%. 18. Binder based on polyester-acrylate according to one of the requirements from 1 to 6 and 13 to 16, indicated by the fact that in them component B has the following meaning B. 90 to 10 wt.% of acrylate resin from b.1) 9.3 to 28.6 wt. % of hydroxyalkyl(meth)acrylates (single or multiple) with 2 to 4 C atoms in the hydroxyl group, individually or in a mixture. b.2) 0 to 63.4 wt.% styrene, b.3) 14.4 to 90.4 wt.% of alkyl (meth)acrylates with 1 to 8 C atoms in the alkyl residue, individually or in a mixture, b.4) 0 to 3.0 wt.% of (meth)acrylic acid, individually or in a mixture, whereby the amounts specified in b.1) b.3) and possibly b.2),) and/ or b.4) supplement up to 100% by weight. 19. Binder based on polyester acrylate according to one of the requirements from 1 to 6 and from 13 to 16, indicated by the fact that in them component B has the following meaning B. 90 to 10 wt. % of acrylate resin from b.1) 17.5 to 53.6 wt. % of hydroxyalkyl(meth)acrylates with 2 to 4 C atoms in the hydroxyl group, individually or in a mixture. b.2) 24 to 60% by weight of styrene, b.3) 12.2 to 62 wt. % of alkyl(meth)acrylate (one or more) with 1 to 8 C atoms in the alkyl residue, individually or in a mixture, b.4) 0 to 4.5 wt. % of (meth)acrylic acid, individually or in a mixture, whereby the amounts specified in b.1) b.2) b.3) and possibly b.4) are supplemented up to 100 wt. %-like. 20. Binder based on polyester acrylate according to one of the requirements from 1 to 6 and from 13 to 16, indicated by the fact that in them component B has the following meaning B. 90 to 10 wt. % of acrylate resin from b.1) 18 to 28.5% by weight of hydroxyalkyl(meth)acrylates with 2 to 4 C atoms in the hydroxyl group, individually or in a mixture. b.2) 0 to 65.4 wt.% styrene, b.3) 20.4 to 82 wt.% of alkyl (meth)acrylates (one or more) with 1 to 8 C atoms in the alkyl residue, individually or in a mixture, b.4) 0 to 5.7 wt. % of (meth)acrylic acid, individually or in a mixture, whereby the amounts specified in b.1), b.3) and possibly b.2),) and/or b.4) are supplemented up to 100 mass % - like that. 21. A process for the production of a polyester-acrylate-based binder according to one of the requirements from 1 to 20, characterized in that polyester A and an organic, inert solvent, boiling point min. 120°C, heat to approximately 120 to approximately 210°C. After that, for 2 to 12 hours, a mixture of monomers and initiators or mixtures of initiators are added at a uniform rate. After the addition is complete, polymerization continues for 2 to 6 hours in the same temperature range. 22. Application of the binder from one of claims 1 to 20, indicated by the fact that it can possibly be used in a mixture with other organic, polyhydroxy compounds, as components of binders for two-component polyurethane varnishes, polyisocyanates for varnishes and possibly commonly contained auxiliaries and additives in polyurethane varnish technology, in the production of varnish coatings on metals, wood, paper, cardboard and plastic mold parts. 23. Use according to claim 22, indicated by the fact that, when it comes to parts of molds made of plastic materials that need to be coated with varnish, it means those molds that are used in the automotive industry. 24. The use of a binder according to one of claims 1 to 20, characterized by the fact that for the production of reactive varnishes, intended for the production of coatings or base coatings, it should be mixed (A) binders, (B) possibly other organic polyhydroxyl compounds, (C) polyisocyanates as crosslinkers and hardeners, (D) inert organic solvents and possibly (E) further additives, common in two-component varnishes. 25. The use of a binder according to one of claims 1 to 20, characterized by the fact that for the production of coatings or primers, a varnish or primer is applied, based on compounds with hydroxyl groups, polyisocyanates, inert organic solvents and possibly, usual additives on the carrier, and then hardens at room or higher temperatures, up to 120°C.