TW201829532A - Radiation-crosslinking polyester and use thereof - Google Patents

Abstract

The present invention relates to polyesters, preferably (meth)acrylic-terminated polyesters, based on a polyester polyol based on di- or polycarboxylic acids and di- or polyols, wherein at least 0.1% by weight of OH- and/or COOH-functionalized polyolefins are present as di- or polycarboxylic acids and/or di- or polyols, based on the sum total of di-or polycarboxylic acids and di- or polyols in the polyester polyol, characterized in that the polyester has at least one, preferably terminal, structural unit of the formula (I), where Y=aliphatic hydrocarbon group and Z=H or CH3, and also use thereof in adhesives or sealants and also in coating compositions.

Description

 Radiation crosslinked polyester and its use  

The present invention relates to a polyester polyol-based polyester based on a di- or poly-carboxylic acid and a di- or poly-alcohol, wherein the di- or poly-carboxylic acid and the di- or poly-alcohol are based on the polyester polyol a sum of at least 0.1% by weight of the OH- and/or COOH-functionalized polyolefin in the form of a di- or polycarboxylic acid and/or a di- or polyhydric alcohol, characterized in that the polyester has at least one structural unit of the formula (I) , Wherein Y = aliphatic hydrocarbon group and Z = H or CH ₃ ; and also for its use in adhesives or sealants and also in coating compositions.

Polyester polyols are now used as raw materials for a variety of purposes, one for the production of adhesives and sealants. These adhesives and sealants can be, for example, thermoplastic or reactive hot melt adhesives, one-pack (1K) or two-pack (2K) liquid adhesives, or epoxy systems.

The advantages of polyester polyols as raw materials for adhesives and sealants are their flexibility and wide range of applications. For example, it is possible to bond wood, textile or metal very well. The disadvantage, however, is that very strong non-polar materials (such as low-energy plastics such as polyethylene or polypropylene) are often unable to bond to polyester-based adhesives due to poor wettability. For such bonding, it is customary to use thermoplastic or decane-modified polyolefins. The problem here is that polyolefins are incompatible or miscible with polyester based systems, and curing of such polyolefin based adhesives typically takes longer. Since the blending of polyolefins is not possible due to lack of compatibility, polyester-based adhesives are combined with polyolefin adhesives to combine the advantages of both systems at present. Such systems will separate due to incompatibility.

The problem solved is therefore to provide a system that avoids the disadvantages of the prior art systems mentioned.

It has been surprisingly found that polyesters as defined in the scope of the patent application solve this problem.

The invention therefore relates to polyester polyol-based polyesters, preferably (meth)acrylic-terminated polyesters, based on di- or polycarboxylic acids and di- or polyhydric alcohols, based on polyester polyols Or a sum of the polycarboxylic acid and the di- or polyhydric alcohol, at least 0.1% by weight of the OH- and/or COOH-functionalized polyolefin is present in the form of a di- or polycarboxylic acid and/or a di- or polyhydric alcohol, characterized in that The polyester has at least one, preferably terminal, structural unit of formula (I), Wherein Y = aliphatic hydrocarbon group and Z = H or CH ₃ ; and also relates to its use in adhesives or sealants as well as in coating compositions. The present invention also provides corresponding adhesives or sealants or formulations as well as corresponding coating compositions and uses thereof.

A disadvantage of the prior art has been unexpectedly discovered, that the low adhesion of the polyester-based adhesive system to low energy surfaces can be overcome by incorporating the polyester used in accordance with the present invention. For example, it is possible to improve the bonding of polar materials to non-polar materials in this way. Thus the polyester according to the invention is bonded to materials of different polarity which can be attributed to the presence of the polyolefin component. The polyesters according to the invention additionally provide the advantage that the non-polar polyolefin structure is rendered compatible by reactive incorporation into the polyester and can be modified in any and multifunctional manner. For example, it is related to molecular weight, thermal properties, and miscibility with other polyesters.

The use of the polyesters according to the invention and the polyesters according to the invention is described below by way of example and is not intended to limit the invention to such illustrative embodiments. Where a range, formula or class of a compound is specified as follows, such intent is intended to encompass not only the corresponding ranges or groups of compounds specifically recited, but also all compounds which may be obtained by omitting individual values (ranges) or compounds. Sub-range and sub-group. Where the document is cited in the context of the present specification, its content will form part of the disclosure of the present invention, especially for the matters referred to. Unless otherwise stated, the percentages specified below are by weight. Unless otherwise stated, for example, the average values specified in the following, the molar mass averages are number averages. Unless otherwise stated, the properties of the materials referred to hereinafter, such as viscosity or the like, are properties of the material at 25 °C. When a chemical (experimental) formula is used in the present invention, the reported index can be an absolute number or an average value. The index associated with the polymeric compound is preferably an average.

According to the polyester of the present invention, preferably the (meth)acrylic-terminated polyester is based on a polyester polyol based on a di- or poly-carboxylic acid and a di- or poly-alcohol, wherein the polyester polyol is based on Or a sum of a polycarboxylic acid and a dihydric or polyhydric alcohol, at least 0.1% by weight of the OH- and/or COOH-functionalized polyolefin, in the form of a di- or polycarboxylic acid and/or a di- or polyhydric alcohol, and characterized in that The polyester has at least one, preferably terminal, structural unit, preferably two or more, as two structural units of formula (I), Wherein Y = aliphatic hydrocarbon group and Z = H or CH ₃ ; and also for its use in adhesives or sealants and also in coating compositions.

In the context of the present invention, the polyester polyol is preferably a randomly distributed (AB) _x system wherein A = di or polycarboxylic acid, B = di or polyhydric alcohol and x > 1 with the proviso that it is based on poly The sum of the di- or polycarboxylic acid and the di- or polyhydric alcohol in the ester polyol, at least 0.1% by weight, preferably at least 5.0% by weight, and especially preferably at least 15% by weight of the OH- and/or COOH-functionalized polyolefin It is present in the form of a di- or polycarboxylic acid A or a di- or polyol B. Thus the polyester polyol may carry OH and/or COOH end groups, preferably OH groups, and preferably have a range of from 1.0 to 10.0, preferably from 1.5 to 5.0, and more preferably from 1.9 to 3.0. Functionality.

In the context of the present invention, any OH- and/or COOH-functionalized, preferably blocked polyolefin known to those skilled in the art can be used in principle as the basis for the polyester polyol. In the context of the present invention, it is preferred to have terminal OH or COOH groups for the formation of polyester polyols.

In the context of the present invention, OH- or COOH-functionalized polyolefins are those polymers which have olefins and/or polyenes as monomers. In the context of the present invention, the repeating unit of the polyolefin consists exclusively of elemental carbon and hydrogen and does not contain an aromatic structure. Thus the polyolefin can comprise any desired double bond ratio.

Examples of suitable OH- and/or COOH-functionalized polyolefins are selected from OH- and/or COOH-functionalized polybutadienes, OH- and/or COOH-functionalized polyisoprene, OH- and/ Or COOH-functionalized polyethylene, OH- and/or COOH-functionalized polyalphaolefins or OH- and/or COOH-functionalized polypropylenes.

The OH- and/or COOH-functionalized polyolefin is preferably an OH-functionalized polyolefin, especially an OH-terminated polybutadiene.

In a particularly preferred embodiment, the OH-functionalized polyolefin is a partially or fully, preferably fully hydrogenated, OH-terminated polybutadiene.

In the context of the present invention, the degree of hydrogenation is determined by the iodine value. In the context of the present invention, the iodine value is measured according to the DGF standard method C-V 11b. The iodine value of the OH- and/or COOH-functionalized polyolefin used in accordance with the invention is up to 260 g iodine per 100 g polymer, preferably up to 100 g iodine per 100 g polymer, especially preferably up to 30 g iodine per 100 g polymer.

The molecular weight of the OH- and/or COOH-functionalized polyolefin used according to the invention is generally from 200 to 20,000 g/mol, preferably from 500 to 15,000 g/mol, particularly preferably from 1000 to 10,000 g/mol.

Molecular weight determination of OH- and/or COOH-functionalized polyolefins was carried out according to DIN 55672-1 using gel permeation chromatography with tetrahydrofuran as the eluent and polystyrene for calibration.

In the context of the present invention, polyolefins which may be used according to preference are commercially available, for example, POLYVEST ® HT from Evonik Resource Efficiency GmbH or NISSO GI-1000, NISSO GI-2000 or NISSO from NIPPON SODA Co., Ltd. GI-3000.

The functionality of the OH- and/or COOH-functionalized polyolefin used is preferably in the range of from 1.9 to 2.2. An important factor in the context of the present invention is the presence of OH and/or COOH groups for forming mixed polyesters. Such groups are typically present at the end of the chain of the polyolefin; in addition, other functional groups may be present along the chain.

In the context of the present invention, the functionality is determined by the dependence of molecular weight on the OH value (OHN) or acid value (AN), according to the following formula:

The functionality of the OH- and/or COOH-functionalized polyolefin or polyester polyol used can be adjusted, for example by reaction of a monoisocyanate with an OH group.

The OH- and/or COOH-functionalized polyolefins described above are polyols or polyacids and are used in accordance with the invention to prepare polyester polyols, preferably by combining with other di- or polyhydric alcohols and two or more The carboxylic acid or its derivative is melt-condensed and synthesized.

With regard to glycols or polyols and dicarboxylic acids or polycarboxylic acids, there are no restrictions in principle, and any mixing ratio is possible in principle. This choice is guided by the desired physical properties of the polyester. At room temperature, these may be solid and amorphous, liquid and amorphous or/and (semi)crystalline.

The di- or polycarboxylic acid used may be any organic acid known to those skilled in the art and containing two or more carboxyl functional groups. In the context of the present invention, a carboxy-functional group is also understood to mean a derivative thereof, such as an ester or an anhydride. The dicarboxylic or polycarboxylic acid may especially be an aromatic or saturated or unsaturated aliphatic or saturated or unsaturated cycloaliphatic dicarboxylic acid or polycarboxylic acid. Difunctional dicarboxylic acids are preferably used.

Examples of suitable aromatic dicarboxylic acids or polycarboxylic acids and derivatives thereof are the following compounds, such as dimethyl terephthalate, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and phthalic anhydride.

Examples of the linear aliphatic dicarboxylic acid or polycarboxylic acid include: oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl succinate, glutaric acid, glutaric acid Dimethyl methacrylate, 3,3-dimethylglutaric acid, adipic acid, dimethyl adipate, pimelic acid, suberic acid, sebacic acid, dimethyl sebacate, sebacic acid, Dimethyl sebacate, undecanedicarboxylic acid, decane-1,10-dibasic acid, dodecane-1,12-dibasic acid, tridecanedioic acid, tetradecane-1,14- Dibasic acids, cetane-1,16-dibasic acids, octadecane-1,18-dibasic acids, dimer fatty acids, and mixtures thereof. Examples of the unsaturated linear dicarboxylic acid and/or polycarboxylic acid include itaconic acid, fumaric acid, maleic acid or maleic anhydride.

Examples of the saturated cycloaliphatic dicarboxylic acid and/or polycarboxylic acid include cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, and cyclohexane-1,2-dicarboxylic acid. derivative.

In principle, any desired diol or polyol can be used for the preparation of the polyester polyol.

Polyol is understood to mean a compound bearing more than two hydroxyl groups. For example, linear or branched aliphatic and/or cycloaliphatic and/or aromatic diols or polyols may be present.

Examples of suitable diols or polyols are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, butane-1,3-diol. Butane-1,2-diol, butane-2,3-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol , decane-1,9-diol, dodecane-1,12-diol, neopentyl glycol, butylethylpropane-1,3-diol, methylpropane-1,3-diol , methyl pentanediol, cyclohexanedimethanol, tricyclo[2.2.1]decane dimethanol, isomer of limonene dimethanol, isosorbide, trimethylolpropane, glycerol, 1,2, 6-hexanetriol, pentaerythritol, polyethylene glycol, polypropylene glycol, and mixtures thereof. Aromatic diols or polyols are understood to mean aromatic polyhydroxy compounds (for example hydroquinone, bisphenol A, bisphenol F dihydroxynaphthalene, etc.) and epoxides (for example ethylene oxide and propylene oxide). The reaction product. The diol or polyol present may also be an ether diol, i.e. an oligomer or polymer based on, for example, ethylene glycol, propylene glycol or butane-1,4-diol. Difunctional diols and dicarboxylic acids are preferably used.

Polyols or polycarboxylic acids having more than two functional groups, such as trimellitic anhydride, trimethylolpropane, pentaerythritol or glycerol, can also be used. Further, a lactone and a hydroxycarboxylic acid can be used as a component of the polyester.

The polyester polyol is preferably synthesized by melt condensation. For this purpose, in each case, one or more of the above-mentioned di- or polycarboxylic acids and di- or polyhydric alcohols are first added in an equivalent ratio of hydroxyl groups of from 0.5 to 1.5, preferably from 1.0 to 1.3, to carboxyl groups. Into and melt. The polycondensation is carried out in a melt preferably at a temperature between 150 ° C and 280 ° C for 3 to 30 hours. During this time, most of the amount of water that is preferably released is first distilled under standard pressure. In other processes, the remaining reaction water and volatile diol are removed until the target molecular weight is reached. Optionally, this can be easily accomplished by depressurization, by expanding the surface area or by passing an inert gas stream through the reaction mixture. The reaction can be additionally accelerated by adding an azeotrope former and/or adding a catalyst before or during the reaction. Examples of suitable azeotrope formers are toluene and xylene. Typical catalysts are organotitanium or organotin compounds such as tetrabutyl titanate or dibutyltin oxide. Catalysts based on other metals such as zinc or ruthenium and metal-free esterification catalysts are also possible. Other additives such as antioxidants or color stabilizers and processing aids are also possible.

The polyester polyol can be characterized by hydroxyl end groups, acid end groups, molecular weight distribution, iodine value, and by means of differential scanning calorimetry.

The hydroxyl end group content determined by titration according to DIN 53240-2 is preferably between 0 and 300 mg KOH/g, preferably between 5 and 50 mg KOH/g.

The acid end group content determined according to DIN EN ISO 2114 is preferably between 0 and 300 mg KOH/g, but preferably less than 2 mg KOH/g.

The number average molecular weight of the polyester polyol is preferably from 500 to 30,000 g/mol, preferably from 1,000 to 20,000 g/mol. It is determined according to DIN 55672-1 by means of gel permeation chromatography using tetrahydrofuran as the eluent and polystyrene for calibration.

The iodine value of the polyester polyol as determined by DGF Standard Method C-B 11b is preferably up to 260 g iodine per 100 g polymer, preferably up to 100 g iodine per 100 g polymer, and most preferably up to 30 g iodine per 100 g polymer.

The thermal properties of the polyester polyol are determined by differential scanning calorimetry (DSC) by the DSC method DIN 53765.

The functionality of the polyester polyol is generally in the range of from 1.0 to 10, preferably in the range of from 1.5 to 5.0 and particularly preferably in the range of from 1.9 to 3.0. In the context of the present invention, functionality is determined by the correlation of molecular weight with OH number (OHN) or acid number (AN).

The polyester, preferably (meth)acrylic terminated polyester according to the invention preferably has formula (II) Wherein P = polyester polyol residue, X = hydrocarbon residue, preferably 1,1,3,3-tetramethylcyclohexane residue, toluene residue or methylene-1,1'-diphenyl residues, Y = aliphatic hydrocarbon chains, Z = H or CH _3, and n = 1 to 10, preferably 2-5.

Preferred polyester has the formula (III) Wherein P' = polyester polyol residue, X' = hydrocarbon residue, 1,1,3,3-tetramethylcyclohexane residue, toluene residue or methylene-1,1'-diphenyl residues, Y '= aliphatic hydrocarbon chain, Z' = H or CH _3, and n '= 1 to 10, preferably 2-3.

The polyester according to the invention can be obtained by a stepwise reaction of one of the polyester polyols described above with a di- or polyisocyanate, which gives an isocyanate-terminated prepolymer and, for example, an OH group-containing (methyl group) a subsequent reaction of the acrylate; or an adduct of one of the polyester polyols described above and a di- or polyisocyanate with an OH group-containing (meth) acrylate, preferably IPDI and (methyl) A reaction of a 1:1 monoadduct of 2-hydroxyethyl acrylate (example, VESTANAT EP DC 1241, Evonik Resource Efficiency GmbH) was obtained. In the simplest case, the polyester polyol is reacted with an isocyanate acrylate at an OH/NCO ratio of 1:0.5 to 1:1.5.

Examples of the (meth) acrylate containing an OH group are 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 3-(acryloxy)-2-(meth)acrylate Hydroxypropyl ester or 4-hydroxybutyl (meth)acrylate.

The di- or polyisocyanates used may be difunctional and/or polyfunctional, aromatic, aliphatic and/or cycloaliphatic isocyanates and carbodiimide-modified isocyanate or isocyanate-terminated prepolymers. Examples of polyisocyanates are diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, toluene diisocyanate isomer, isophorone diisocyanate, hexamethylene diisocyanate, Dicyclohexylmethane 4,4'-diisocyanate and mixtures thereof. It is especially preferred to be an aliphatic polyisocyanate.

The polyesters according to the invention may be used alone or in combination with other input materials as a component of a radiation cross-linking adhesive formulation, a sealant formulation or a coating formulation.

The invention therefore further provides a radiation crosslinkable adhesive or sealant formulation comprising at least a polyester according to the invention, preferably a (meth)acrylic terminated polyester.

Furthermore, the adhesive or sealant formulation according to the invention may contain at least one other (meth)acrylic functionalized polymer, in particular based on OH-functionalized polyesters, OH-functionalized polyethers, OH-functionalized poly-polymers. Butadiene (eg POLYVEST ^® HT) and OH-functionalized poly(meth)acrylate.

The additionally used (meth)acrylic functionalized polymers are in principle freely selectable and are known in principle from the prior art to those skilled in the art.

It is preferred to use (meth)acrylic acid functionalized polyester or (meth)acrylic acid functionalized polybutadiene as the other component in the adhesive or sealant formulation according to the invention, particularly preferably polyester. In a preferred embodiment of the present invention, at least one other polymer is selected from the group consisting of polyesters, preferably synthesized by melt condensation of a di- or polyhydric alcohol and a di- or polycarboxylic acid or a derivative thereof, or It has been prepared by ring opening polymerization.

The adhesive or sealant formulation according to the present invention is preferably a single package of radiation crosslinked polyurethane adhesive.

The polyester according to the invention, preferably the (meth)acrylic terminated polyester, is present in the formulation in a proportion of from 1 to 99% by weight, preferably from 5 to 85% by weight and particularly preferably 10, based on the total formulation. -70% by weight.

In addition to the polyesters used in accordance with the invention and possibly other polymers, the adhesive formulation may contain up to 50% by weight of other additives, based on the total formulation.

Such additives may be: monofunctional polymers such as thermoplastic polyurethanes (TPU) and/or polyacrylates and/or ethylene-vinyl acetate copolymers (EVA); pigments or fillers such as talc, cerium oxide, Titanium dioxide, barium sulfate, calcium carbonate, carbon black or color pigments; tackifiers such as rosins, hydrocarbon resins, phenolic resins; and aging stabilizers and auxiliaries.

In a preferred embodiment of the invention, the adhesive or sealant formulation comprises, in particular, from 5 to 75% by weight of the preferred (meth)acrylic terminated polyester of the invention, and in particular 25-95 % by weight of a mixture of at least one other polyester, and at least one polyisocyanate wherein the ratio of NCO:OH of the polyester to isocyanate is from 2.0 to 3.5. The formulation may optionally contain up to 50% by weight of filler. In summary, the proportion of individual components amounts to 100% by weight.

The above adhesive system may be applied at a temperature between room temperature and 200 ° C, preferably between 80 ° C and 150 ° C, depending on the viscosity of the respective formulation.

The invention further provides for the use of an adhesive or sealant formulation according to the invention for bonding or sealing a substrate, in particular for bonding or sealing a non-polar substrate.

Adhesive or sealant formulations according to the present invention are particularly suitable for use in the production of adhesives for various substrates, such as plastics, metals, various types of wood, mineral substrates (such as asphalt, concrete), especially for metal substrates and textiles. Bonding, and especially for the bonding of various plastics. The nature and extent of bonding are not limited.

Unexpectedly, the formulations according to the invention are suitable for use on non-polar surfaces.

In a preferred embodiment, the substrate bonded according to the present invention is a substrate having a surface tension of less than 40 mN/m, preferably less than 35 mN/m, such as polyethylene or polypropylene. The surface tension is determined in the context of the invention in accordance with DIN 55660-2.

Preferably, the bond is a bond in the wood and furniture industry (eg, assembly bonding and decorative film lamination to the fiberboard); in the automotive sector (eg, film or textile laminated to the side of the door, interior roof) Lining; seat manufacturing and retainer bonding; installable components in (semi) structural sections; fiber reinforced composites or/and metals); in the construction industry, footwear industry and textile industry (eg deuterated or hydrophobic) In textiles; and in windows (for example for contour jackets). Furthermore, the adhesives according to the invention are suitable as sealants in the packaging industry and as coating materials, particularly in the electrical industry.

Adhesive formulations according to the present invention can be applied by all known methods, for example by means of extruders, beads, nozzles, diffusion, dipping, injecting, pouring, rolling, spraying, printing, wiping, washing, tumbling, Centrifuge or in powder (electrostatic) form.

The invention therefore further provides a coating composition comprising at least a polyester according to the invention, preferably a (meth)acrylic terminated polyester. Preferably, it is in the form of a single package of radiation crosslinked polyurethane coating or acrylate coating.

Furthermore, the coating composition according to the invention may contain at least one further (meth)acrylic functionalized polymer, in particular based on OH-functionalized polyesters, OH-functionalized polyethers, OH-functionalized polybutadienes ( For example, POLYVEST ^® HT) and OH- and/or COOH-functionalized poly(meth)acrylates.

The additionally used acrylic acid functionalized polymers are in principle freely selectable and are known in principle from the prior art to those skilled in the art.

It is preferred to use (meth)acrylic acid functionalized polyester or (meth)acrylic acid functionalized polybutadiene as the other polymer, and polyester is particularly preferably used. In a preferred embodiment of the invention, the at least one other (meth)acrylic acid functionalized polymer is selected from the group consisting of polyesters, preferably by di- or polyhydric alcohols and di- or polycarboxylic acids or derivatives thereof. The melt condensation synthesis of the material, or it has been prepared by ring opening polymerization. In addition, the polyester has in particular a linear or branched structure and is preferably slightly branched.

The proportion of the polyester, preferably (meth)acrylic terminated polyester, in the formulation according to the invention is from 0.1 to 99% by weight, preferably from 0.1 to 50% by weight, and especially preferably 0.1, based on the total formulation. -25% by weight.

Additionally, the coating composition can comprise cross-linking components that are known to those skilled in the art from the prior art and that require crosslinking.

As well as the coating compositions already described, the present invention also provides a method of coating a substrate, particularly preferably for coating a metal substrate. In the method for coating a substrate according to the present invention, the substrate is coated with the coating composition according to the present invention as described above, and then the coating is dried and/or calcined. During this operation, the formulation components are crosslinked to form a coating according to the present invention.

There are a plurality of specific examples regarding a method of coating a substrate using the coating composition according to the present invention. In the simplest embodiment, the coating is performed directly on the substrate. Particularly useful for this purpose is the method of applying a formulation according to the invention in the form of an organic solution, together with other formulation components, as an "organosol" to the substrate, and subsequently drying the coated layer. The coating takes place here, for example, by means of knife coating, roll coating, dip coating, curtain coating or spraying. Crosslinking of the coating occurs at the same time as the drying operation.

Optionally, the coating according to the invention may be provided with one or more other functional layers. The layer in question may comprise, for example, an anti-scratch coating, a conductive layer, an anti-contamination coating and/or a reflection enhancing layer or other layer having optical function. These additional layers can be applied, for example, by means of physical vapour deposition (PVD) or chemical vapour deposition (CVD).

Additional scratch resistant coatings may be applied as appropriate to further improve scratch resistance. The anti-scratch coating can be, for example, a ruthenium oxide layer that is directly coated by means of PVD or CVD.

The above description can be most widely used by those skilled in the art, even without further explanation. The preferred embodiments and examples are to be understood as illustrative only and not in any way limiting. The invention is illustrated in more detail below using examples. Alternative embodiments of the invention are similarly obtained.

Example:

Measurement method:

Gel permeation chromatography

The number average molecular weight of the mixed polyester according to the invention and the polyolefin used according to the invention is determined according to DIN 55672-1 by means of gel permeation chromatography, with tetrahydrofuran as the eluent and polystyrene for calibration.

2. Differential scanning calorimetry

The thermal properties of the mixed polyester used in the context of the present invention are determined by differential scanning calorimetry (DSC) using the DSC method DIN 53765.

3.OHN

The polyester prepared may have a hydroxyl group as a terminal group. The concentration of the OH group (mg KOH/g polymer) was determined by titration according to DIN 53240-2.

4. Acid value

The concentration of the acid end groups (mg KOH/g polymer) was determined by titration according to DIN EN ISO 2114.

5.NCO value

The NCO value (% by weight) of the reaction product of the prepared polyester polyol and isocyanate is determined by titration according to DIN EN 1242.

6. Tensile shear strength

The adhesive properties of the prepared adhesive formulations (N) were measured by means of a floating roll peel test based on DIN EN 2850.

Preparation of polyester polyols:

Synthesis of polyester polyol P1:

In a 2 L flask with a distillation connection, 702 g of adipic acid (4.81 mol) were melted together with 526 g of neopentyl glycol (5.06 mol) and 465 g of NISSO G1-1000 (about 0.27 mol) under nitrogen. At a reaction temperature of 245 ° C, most of the water formed is distilled off in about two to four hours. Subsequently, 0.15 titanium catalyst was added and the pressure was reduced stepwise to 10 mbar at the same temperature. When the acid end group (acid value <1 mg KOH/g) is no longer present, the reaction has ended and the content of 30 mg KOH/g hydroxyl end group has been reached. The glass transition point of the polyester polyol was -49 °C.

Synthesis of polyester polyol P2:

995 g of adipic acid (6.82 mol) were melted together with 779 g of neopentyl glycol (7.49 mol) in a 2 liter flask with a distillation connection under nitrogen. At a reaction temperature of 245 ° C, most of the water formed is distilled off in about two to four hours. Subsequently, 0.15 titanium catalyst was added and the pressure was reduced stepwise to 10 mbar at the same temperature. When the acid end group (acid value <1 mg KOH/g) is no longer present, the reaction has ended and the content of 30 mg KOH/g hydroxyl end group has been reached. The glass transition point of the polyester polyol was -46 °C.

General procedure for the preparation of radiation crosslinked polyester:

In a 1 liter glass flask, the specified amount of polyol in Table 1 was blended with 0.3 g of dibutyltin laurate (DBTL) as a catalyst, and homogenized at 60 ° C under a nitrogen atmosphere. Subsequently, the amount of VESTANAT EP DC 1241 (NCO value 11.8%, NCO: OH ratio 1:1) specified in Table 1 was slowly added dropwise with continuous stirring. After completion of the addition of VESTANAT EP DC 1241, the reaction was stirred and maintained at 60 °C until the NCO value was <0.1%.

Crosslinking of radiation crosslinked polyester:

The above acrylic terminated polymers 1 and 2 were each blended with 2.0% by weight of Omnirad 1173 as a photoinitiator and heated to 100 °C. Subsequently, the polymer was applied to a crepe paper and taken out in the form of a film using a 100 μm doctor blade. The crepe paper with the polymer was then irradiated at a strength of 65 J/cm ² in a UV belt dryer (UN50023 from Technigraf GmbH). A self-adhesive film is obtained. Successful cross-linking of the polymer film was explored and confirmed by the addition of a small film sample to acetone which did not dissolve even after several days.

Adhesive properties of radiation crosslinked polyester:

The adhesion properties of the radiation crosslinked self-adhesive film were investigated on different substrates by means of 90° peeling and are reported in Table 2.

It is clearly shown that the adhesion value of the embodiment of the present invention has a significantly improved adhesion to a non-polar material such as PP due to the ratio of polyolefin, while always having good adhesion to polar metals.

Claims (15)

A polyester polyol-based polyester based on a di- or poly-carboxylic acid and a di- or poly-alcohol, wherein the sum of the di- or poly-carboxylic acid and the di- or polyhydric alcohol in the polyester polyol is based on At least 0.1% by weight of the OH- and/or COOH-functionalized polyolefin is present in the form of a di- or polycarboxylic acid and/or a di- or polyhydric alcohol, characterized in that the polyester has at least one structural unit of the formula (I), Where Y = an aliphatic hydrocarbon group, and Z = H or CH _3. The polyester of claim 1, wherein the polyester has the formula (II), Wherein P = polyester polyol residue; X = hydrocarbon residue, preferably 1,1,3,3-tetramethylcyclohexane residue, toluene residue or methylene-1,1'-di a benzene residue; Y = an aliphatic hydrocarbon chain; Z = H or CH ₃ ; and n = 1 to 10, preferably 2 to 5. A polyester according to claim 1 or 2, wherein the polyester has the formula (III), Wherein P' = polyester polyol residue; X' = hydrocarbon residue, preferably 1,1,3,3-tetramethylcyclohexane residue, toluene residue or methylene-1,1' - diphenyl residue; Y '= aliphatic hydrocarbon chain; Z' = H or CH _3; and n '= 1 to 10, preferably 2 to 3.  A polyester according to one or more of claims 1 to 3, wherein the OH- and/or COOH-functionalized polyolefin is selected from the group consisting of OH- and/or COOH-functionalized polybutadiene. , which may also exhibit partial or complete hydrogenation; OH- and/or COOH-functionalized polyisoprene, which may also exhibit partial or complete hydrogenation; OH- and/or COOH-functionalized polyethylene; OH- and / Or a COOH-functionalized polyalphaolefin; or an OH- and/or COOH-functionalized polypropylene.    A polyester according to one or more of claims 1 to 4, wherein the OH- and/or COOH-functionalized polyolefin is an OH-terminated polybutadiene, which may also be partially or Completely hydrogenated.    The polyester of any one of claims 1 to 5, wherein the molecular weight of the OH- and/or COOH-functionalized polyolefin is from 200 to 20,000 g/mol as determined according to DIN 55672-1.    A use of a polyester as claimed in one or more of claims 1 to 6 for use in a radiation crosslinking adhesive, or a sealant or coating composition.    An adhesive or sealant formulation comprising at least one or more polyesters according to one or more of claims 1 to 6.    An adhesive or sealant formulation according to claim 8 wherein the adhesive or sealant formulation is a single package of radiation crosslinked polyurethane adhesive.    An use of an adhesive or sealant formulation as claimed in claim 8 or 9 for bonding a substrate, preferably a non-polar substrate.    The use of claim 10, wherein the substrates are substrates having a surface tension of less than 40 mN/m as determined according to DIN 55660-2.    A coating composition comprising at least one or more polyesters according to one or more of claims 1 to 6.    The coating composition of claim 12, wherein the coating composition is a single package of radiation crosslinked polyurethane coating or acrylate coating.    A use of a coating composition according to claim 12 or 13 for coating a metal substrate.    For use in the scope of claim 14, wherein the contact angle of the coatings is >90° according to DIN 55660-6.