TPO Primer

Abstract

A composition in the form of a solution or dispersion comprising an anhydride-modified polyolefin, an anhydride-modified styrene block copolymer, and an isocyanate-containing crosslinker, wherein the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer are present in a combined amount of 7 wt% to 18 wt% of the composition, the weight ratio of the anhydride-modified polyolefin to the anhydride-modified styrene block copolymer being in the range of 2:1 to 6:1, the weight ratio of the combined anhydride-modified polyolefin and the anhydride-modified styrene block copolymer to the isocyanate-containing crosslinker being in the range of 0.2:1 to 0.5:1, and the solvent includes a ketone as a first solvent and an alkylbenzene or alkane solvent. The composition can be used for bonding TPO to TPU, polyester, or PU. The composition can be used for bonding a first TPO component or coating to a second TPU, polyester, or PU component by applying heat and, optionally, pressure, and the resulting adhesion improves peel strength.

Description

[Technical Field]

[0001] The present invention relates to a primer for bonding dissimilar plastic pairs, which are TPO / polyester, TPO / TPU, and TPO / PU. [Background technology]

[0002] TPO is used in a variety of industrial applications. For example, it is used in the form of a recovery film, or membrane, as a covering layer on building roofs to provide water resistance. TPO is also increasingly being used in the automotive industry, where many components, such as bumpers, are now made from TPO to reduce weight. TPO itself has the well-known drawback of not adhering well to substrates made from other materials due to its low surface energy.

[0003] The traditional method of adhering TPO sheets to substrates of other materials has been by simple mechanical joints such as rivets, screws, or nails, which do not form an intimate contact between the TPO layer and the substrate over the entire interface.

[0004] Conveyor belts with a TPO cover layer bonded to a fibrous traction layer are known. Examples include the Cleanline® series conveyor belts sold by the applicant at the time of filing. The fibrous traction layer is a woven fabric consisting of monofilament weft yarns and spunbond warp yarns. The rough, napped surface and the fiber ends of the spunbond warp fibers allow for intimate physical entanglement between the TPO and the woven fabric, compensating for the poor adhesion between the TPO and the woven fabric. However, spunbond fibers have very low tenacity. Therefore, such conveyor belts typically have a low tensile strength at 1% elongation in the relaxed state (k1% relaxed) of only 3-5 N / mm, limiting the weight of the load they can carry. This limitation becomes more problematic as the length of the conveyor belt increases, as the weight of the transported load causes the belt to bend downward more significantly. Therefore, such belts are suitable for light-weight food applications. For heavier load and / or longer length applications, thus requiring belts with k1% relaxation values ​​typically in the range of 8-12 N / mm, the use of spunbond fabrics as traction layers becomes more difficult.

[0005] In the field of building roofs, it is known that damaged or aged TPO-based roofs can be overcoated for repair purposes with water-based or solvent-based acrylic latex coating solutions that adhere to the TPO and crosslink to elastomers. According to corresponding internet advertisements (e.g., Arkema Coating Resins), adhesion of acrylic latex appears to be significantly better on aged TPO than on new TPO, suggesting that the TPO must undergo surface modification by atmospheric oxidation and / or UV degradation before such acrylic latexes can be applied safely.

[0006] In the above-mentioned field of the automobile industry, it is also known to overpaint TPO components, and the paint is applied to the TPO components via an adhesion promoter containing chlorinated polypropylene as the main active ingredient (see, for example, Non-Patent Document 1).

[0007] Maleic anhydride-modified ("maleated") polyolefins are commercially available, such as Amplify™ and Fusabond® (Dow), and Orevac® (Arkema) types. Similarly, maleic anhydride-modified ("maleated") styrene block copolymers are commercially available, such as Kraton™ (Kraton or Shell) SEBS-based types.

[0008] It is known that isocyanates and carboxylic anhydrides or carboxylic acids react with each other to give polyamides or polyamide-imides, respectively, especially in the presence of a suitable catalyst (see, for example, Patent Document 1). The products thus obtained are particularly suitable as coating compositions. They can be used as impregnating resins or applied to various substrates, such as textiles and other polymeric materials.

[0009] Patent Document 2 discloses a composition containing a functionalized styrene block copolymer, a functionalized ethylene / α-olefin interpolymer, and an isocyanate component, and also containing a hydrocarbon solvent and a polar solvent which may be a ketone. This composition can be used as a primer for an article containing, inter alia, a PET layer and, optionally, a polyolefin layer. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] U.S. Patent No. 4,156,065 [Patent Document 2] International Publication No. 2017-003600 [Patent Document 3] International Publication No. 94 / 15981 [Non-patent literature]

[0011] [Non-Patent Document 1] Mirabella et al., Polymer Engineering and Science, Vol. 40(9), pp. 2000-2006 (2004) [Non-patent document 2] Ghaemy, M., Roohina, S, Iranian Polymer Journal 12(1), pp. 21ff. (2003) [Non-patent document 3] Siggia, S., and Gordon Hanna, J, Anal. Chem. 23(11), p. 1717ff. (1951) [Non-patent document 4] in Dann, JR, J. Colloid Interf. Sci. 32(2) pp. 302 ff. (1970) Summary of the Invention [Problem to be solved by the invention]

[0012] Therefore, there remains a need for an adhesion primer that will generally allow TPO components or layers to adhere to components or coatings made of plastics other than TPO, such as TPU, polyester (especially PET), or PU. [Means for solving the problem]

[0013] The present invention provides the following: 1. Anhydride modified polyolefin, an anhydride-modified styrene block copolymer, and Isocyanate-containing crosslinking agents A composition comprising: 2. Anhydride-modified polyolefin 1) a polyolefin selected from the group consisting of polyethylene, ethylene-α-olefin copolymers (wherein the α-olefin is selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene), and polypropylene; maleic anhydride, Diels-Alder reaction products of maleic anhydride with buta-1,3-diene, cyclopentadiene, or cyclohexa-1,3-diene, and reaction products of maleic anhydride with α-olefins selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene; or by grafting with an olefin anhydride selected from the group consisting of 2) The composition according to the above item [1], which is obtained by copolymerizing an olefin anhydride as defined above with ethylene and / or an α-olefin as defined above. 3. The composition of [1] or [2] above, wherein the styrene block copolymer in the anhydride-modified styrene block copolymer is selected from the group consisting of SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), and SEBS (styrene-(ethylene-co-butylene)-styrene). 4. The composition according to any one of [1] to [3] above, wherein the total amount of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer is in the range of 7% by weight to 18% by weight based on the total amount of the composition, and the weight ratio of the anhydride-modified polyolefin to the anhydride-modified styrene block copolymer is in the range of 2:1 to 6:1. 5. The isocyanate-containing crosslinking agent is i) reaction products obtained by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst, followed by reacting the resulting homogeneous mixture of aniline-formaldehyde adducts with phosgene; ii) selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, diisophorone diisocyanate, and diphenyl ether-2,4,4-triisocyanate; or iii) Uretidinedione- and / or 2,4,6-trioxotriazine-containing oligomers of 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate. The composition according to any one of the above [1] to [4], 6. The composition according to any one of the above [1] to [5], wherein the weight ratio of the isocyanate-containing crosslinking agent to the sum of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer is in the range of 0.2:1 to 0.5:1. 7. The composition according to any one of [1] to [6] above, which is in the form of a solution or dispersion in a solvent. 8. The solvent has the following formula: [ka] [In the formula, R 1 and R 2 are each independently selected from the group consisting of methyl, ethyl, and branched or straight chain C-C alkyl; 1 and R 2 the total carbon number of R is in the range of 4 to 7; or 1 and R 2 is bonded to -(CH2) m - (wherein m is an integer of 4 to 7). and a second component, either one or more alkylbenzene solvents which are mono- to tri-(C1-C3-alkyl)benzenes or C6-C8 alkane solvents, each having a boiling point in the range of 110°C to 170°C. 9. The composition according to [8] above, wherein the first component of the solvent is cyclohexanone and the second component of the solvent is methylcyclohexane or a mixture of xylene and ethylbenzene. 10. a) the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer are present in a combined amount ranging from 7% to 18% by weight based on the total weight of the composition, and the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer are present in a weight ratio ranging from 2:1 to 6:1; the isocyanate-containing crosslinker is present in a weight ratio relative to the sum of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer in the range of 0.2:1 to 0.5:1; The solvent is a mixture of an alkyl solvent (especially methylcyclohexane) and a ketone solvent (especially cyclohexanone), with the weight ratio of alkyl solvent to ketone solvent ranging from 15:1 to 30:1; or b) the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer are present in a combined amount ranging from 7% to 11% by weight based on the total weight of the composition, and the weight ratio of the anhydride-modified polyolefin to the anhydride-modified styrene block copolymer is ranging from 2:1 to 6:1; the isocyanate-containing crosslinking agent is a reaction product obtained by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst, and then reacting the resulting homogeneous aniline-formaldehyde adduct mixture with phosgene to convert the aromatic amine groups to isocyanate groups, and the isocyanate-containing crosslinking agent is present in a weight ratio of 0.2:1 to 0.5:1 based on the total weight of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer; and The solvent is a mixture of alkylbenzene solvent and ketone solvent, where the alkylbenzene solvent (particularly a mixture of xylene and ethylbenzene in a weight ratio of 3:1 to 2:1) and the ketone solvent (particularly cyclohexanone) are in a weight ratio ranging from 6:1 to 3:1. The composition according to [9] above, wherein 11. To promote adhesion between TPO and TPU, polyester, or PU, Anhydrous modified polyolefin, an anhydride-modified styrene block copolymer, and A complex of an isocyanate-containing crosslinker or the use of a composition according to any one of [1] to

[10] above. 12. The use according to

[11] above, wherein the anhydride-modified polyolefin is as defined in [2] above; the anhydride-modified styrene block copolymer is as defined in [3] above; the isocyanate-containing crosslinking agent is as defined in [5] above; the total amount of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer in the composition and the weight ratio of the anhydride-modified polyolefin to the anhydride-modified styrene block copolymer are as defined in [4] above; the weight ratio of the isocyanate-containing crosslinking agent to the total of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer is as defined in [6] above; or the composition is as defined in any one of [7] to

[10] above. 13. A method for bonding, by heat and optionally pressure, a first surface of a first part of TPO to a second surface of a second part of polyester or TPU, comprising the steps of: Anhydrous modified polyolefin, an anhydride-modified styrene block copolymer, and Isocyanate-containing crosslinking agents or the composition according to any one of [1] to

[10] above to the first surface and / or the second surface; and Bonding a first surface coated with the combination or composition to a second surface, or a first surface to a second surface coated with the combination or composition, or a first surface coated with the combination or composition to a second surface coated with the combination or composition by applying heat and optionally pressure. A method comprising: 14. The method according to

[13] above, wherein during bonding of the first and second surfaces, the first and second surfaces are heated to a temperature 20°C to 50°C, preferably 30°C to 40°C, higher than the melting point of the TPO of the first part, wherein the melting point is measured by differential scanning calorimetry (DSC) in accordance with ISO standard 11357-3. 15. A method for bonding a first coating of TPO to a second surface of a second part of polyester or TPU by extrusion and melt coating, comprising the steps of: Anhydride modified polyolefins; anhydride-modified styrene block copolymers; and isocyanate-containing crosslinkers; or applying to the second surface a composition according to any one of [1] to

[10] above; and Extrusion and melt coating of TPO onto a second surface coated with the combination or composition. A method comprising: 16. A method for bonding a second coating of TPU to a first surface of a first part of TPO by extrusion and melt coating, comprising the steps of: Anhydride modified polyolefins; Anhydrous modified styrene block copolymers; and isocyanate-containing crosslinkers; or applying to the first surface a composition according to any one of [1] to

[10] above; and Extrusion and melt coating of TPO onto a first surface coated with the combination or composition. A method comprising: 17. A method for bonding a second coating of crosslinkable PU to a first surface of a first part of TPO by applying heat and, optionally, pressure, comprising the steps of: Anhydride modified polyolefins; Anhydrous modified styrene block copolymers; and isocyanate-containing crosslinkers; or applying a crosslinkable TPU to a first surface coated with the composition according to any one of [1] to

[10] above; and adhering a crosslinkable TPU to the composite or the first surface coated with the composition by applying heat and, optionally, pressure, while simultaneously crosslinking the crosslinkable PU to a crosslinked PU. A method comprising: 18. The method according to

[17] above, wherein the crosslinkable PU is applied as a solution in a solvent and the solvent is evaporated before bonding by heating and optionally applying pressure. 19. The method according to any one of

[13] to

[18] above, wherein the combination or composition is applied to the first surface and / or the second surface in a dry weight of 10 to 40 g per square meter of the total area of ​​the first surface and / or the second surface. DETAILED DESCRIPTION OF THE INVENTION

[0014] The compositions and combinations of the present invention primarily include anhydride-modified polyolefins. By "water-modified polyolefins," we mean polyolefins lacking anhydride moieties, to which anhydride-containing side chains or anhydride-containing moieties have been grafted. The polyolefins modified here are preferably polyethylene, ethylene-α-olefin copolymers (wherein the α-olefin is selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene), or polypropylene, more preferably polyethylene or polypropylene. The grafting reaction is preferably carried out by a free radical mechanism. This is typically carried out in the molten state of the starting polyolefin, preferably at a temperature ranging from the melting point of the starting polyolefin to 260°C (if the starting polymer has a sharp melting point) or from the upper temperature boundary of the melting range of the starting polyolefin to 260°C (if the starting polyolefin has a melting range). Grafting can be carried out by mixing the molten starting polyolefin with a free-radical initiator and an olefinic anhydride in a Banbury mixer or extruder for a time typically ranging from 20 seconds to 2 minutes. The initiator is usually a thermal initiator, such as a diacyl peroxide, α-oxy- and α-peroxyhydroperoxide, or a hydroperoxide, preferably dibenzoyl peroxide. The olefinic anhydride is preferably selected from the group consisting of maleic anhydride; Diels-Alder reaction products of maleic anhydride with buta-1,3-diene, cyclopentadiene, or cyclohexa-1,3-diene; and reaction products of maleic anhydride with one of the α-olefins listed above (the latter reaction products are known in the art as "alkenyl succinic anhydrides"). The amount of initiator is preferably in the range of 0.1 to 0.5 wt. % based on the starting polyolefin. The amount of the olefin anhydride is usually 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the starting polyolefin.This free radical grafting, especially when carried out with maleic anhydride itself, can also be carried out in the presence of α-olefins (as exemplified above) and styrene as comonomers, as described in US Pat. No. 5,629,999.

[0015] "Anhydride-modified polyolefins" are understood in the context of the present invention to mean polyolefins in which the above-listed olefin anhydrides are copolymerized directly as comonomers with ethylene and / or the above-listed α-olefins by a free radical mechanism customarily used in the art.

[0016] In either of the above two meanings of "anhydride-modified polyolefin," the amount of the anhydride moiety (-C(O)-O-(O)-C-) is preferably 0.1 to 5 wt %, more preferably 0.5 to 2 wt %, based on the anhydride-modified polyolefin. Here, the amount of the anhydride moiety can be measured by quantitative titration of a potassium methoxide solution in methanol.

[0017] As mentioned in the introduction of this specification, commercially available maleated polyolefins are also suitable for the purposes of the present invention.

[0018] For purposes of the present invention, the anhydride-modified polyolefin is preferably thermoplastic, i.e., not chemically crosslinked or only weakly crosslinked to maintain solubility at useful concentrations in the solvents contemplated for preparing the compositions of the present invention. The melt flow rate (MFR) of the anhydride-modified polyolefin is preferably in the range of 0.5 to 40 g / 10 min, more preferably 1 to 20 g / 10 min, under a 2.16 kg load. The MFR is measured at a melting temperature of 190°C for anhydride-modified polyolefins having a melting point below 150°C or a melting range entirely below 150°C; and at a melting temperature of 230°C for anhydride-modified polyolefins having a melting point of 150°C or higher or a melting range with a lower temperature boundary of 150°C or higher.

[0019] The compositions and combinations of the present invention secondly include an anhydride-modified styrene block copolymer. The styrene block copolymer itself is conventionally known and is obtained by ionic copolymerization of styrene with a 1,3-diolefin and optionally ethylene. The styrene block copolymer is preferably selected from the group consisting of SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), and SEBS (styrene-(ethylene-co-butylene)-styrene), and most preferably SEBS.

[0020] An "anhydride-modified styrene block copolymer" is understood to mean a styrene block copolymer lacking an anhydride moiety to which an anhydride-containing side chain or an anhydride-containing moiety has been grafted. The starting styrene block copolymer to be modified preferably contains 20 to 70 wt. %, more preferably 25 to 50 wt. % of polystyrene block sequences, based on the total weight of the starting styrene block copolymer. The grafting reaction can be carried out in a manner similar to that described above for the anhydride-modified polyolefin.

[0021] A preferred embodiment of the content of anhydride moieties in the anhydride-modified styrene block copolymer and a method for measuring the content are as described above for the anhydride-modified polyolefin.

[0022] For purposes of the present invention, the anhydride-modified styrene block copolymer is a thermoplastic or thermoplastic elastomer, i.e., uncrosslinked or only weakly chemically crosslinked to maintain solubility at useful concentrations in the solvents contemplated for preparing the compositions of the present invention. The melt flow rate (MFR) of the anhydride-modified styrene block copolymer is preferably in the range of 5 to 50 g / 10 min, more preferably 10 to 40 g / 10 min, under a 5 kg load and at a melting temperature of 230°C.

[0023] As mentioned in the introduction to this specification, commercially available maleated styrene block copolymers are also suitable for the purposes of this invention.

[0024] The weight ratio of anhydride-modified polyolefin to anhydride-modified styrene block copolymer in the compositions and combinations of the present invention is preferably in the range of 2:1 to 6:1, more preferably in the range of 3:1 to 5:1, and most preferably in the range of 3.5:1 to 4.5:1.

[0025] The composition of the present invention thirdly includes an isocyanate-containing crosslinker. The term "crosslinker" has the general meaning of a compound capable of forming a covalent bond between two polymer chains and therefore requires two or more functional groups capable of reacting with the two polymer chains. Therefore, for the purposes of the present invention, the crosslinker is a compound having two or more NCO functional groups, preferably three or more NCO functional groups. Aliphatic and / or aromatic polyisocyanates are particularly suitable. Polyisocyanates of the above types include, inter alia, biuretized polyisocyanates, optionally containing uretidinedione-containing polyisocyanates of aliphatic or cycloaliphatic diisocyanates such as hexane diisocyanate and / or isophorone diisocyanate, cyanurates of hexane diisocyanate, isophorone diisocyanate, 2,4- / 2,6-toluylene diisocyanate, or, optionally, mixtures of polyisocyanates or mixed polymerized polyisocyanates. Also suitable are reaction products of trimethylolpropane, glycerol, pentaerythritol, or other polyols with a molar excess of toluylene diisocyanate, diphenylmethane diisocyanate, or isomeric mixtures thereof, in admixture with dialcohols such as diethylene glycol, 1,4-butanediol, dipropylene glycol, and other diols, and reaction products of di- and tri-ethylene glycol, di- and tri-propylene glycol with a molar excess of toluylene diisocyanate, or diphenylmethane diisocyanate, alone or in mixtures.

[0026] Preferably, the isocyanate-containing crosslinker is one of the following (i) to (iii): i) reaction products obtained by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst, and then reacting the resulting homogeneous aniline-formaldehyde adduct mixture with phosgene to convert the aromatic amine groups to isocyanate groups, the reaction products being conventional and each having essentially the following structural formula: [ka] [In the formula, n is preferably an integer ranging from 0 to 20, more preferably from 1 to 10, and the methylene chain may be in the ortho, meta, or para position relative to the NCO group.] It is believed that the compound is a mixture of compounds represented by the formula: ii) 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, meta-tetramethylxylylene diisocyanate, trans-cyclohexane diisocyanate, isophorone diisocyanate, or diphenyl ether-2,4,4-triisocyanate. iii) Uretidinedione- and / or 2,4,6-trioxotriazine-containing oligomers of 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate, which may have the following structure (I): [ka] wherein X is a direct bond forming a uretidinedione; or the following structure (II): [ka] wherein in the above structures (I) and (II): on each phenyl ring, the two NCO-containing substituents are meta to each other; and the methyl substituent is either ortho to both NCO-containing substituents, or ortho to one of the NCO-containing substituents and para to the other NCO-containing substituent; and -Y is a direct bond or a further divalent radical of structure (II) above that forms another uretidinedione, or structure (III) below: [ka] wherein all symbols are as defined above in structures (I) and (II). is a divalent group that forms another 2,4,6-trioxotriazine represented by the formula: However, the oligomer of structure (I) remains soluble in the solvent of the composition at the concentrations required in the present invention, which means that the oligomer of structure (I) preferably has a molecular weight of m×174.2 g / mol or less, where m is 7, preferably 5.

[0027] Most preferably, in the above structure (I), X and all Y's are direct bonds, i.e., the compound represented by structure (I) is a dimer of 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate; or, X is a divalent group represented by the above structure (II), and all Y's are direct bonds, i.e., the compound represented by structure (I) is a trimer of 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate.

[0028] These oligomers can be conventionally obtained, for example, by reacting 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate in a suitable solvent such as toluene and / or ortho-dichlorobenzene in the presence of a catalytic amount of pyridine at room temperature, optionally followed by heating to a temperature in the range of 40° C. to 100° C. to control the molecular weight of the oligomer. Such oligomers in which m is 3, 5, or 7 are known and are registered under EC Registration No. 938-708-5.

[0029] The NCO content in the isolated starting isocyanate-containing crosslinker is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, based on the isocyanate-containing crosslinker. For the purposes of the present invention, this determination can be carried out at room temperature according to DIN standard 11909 (2007).

[0030] For purposes of the present invention, the content of anhydrous moieties (—C(O)—O—(O)—C—) in the isolated anhydride-modified polyolefin or isolated anhydride-modified styrene block copolymer starting material can be determined according to the method described in Non-Patent Document 2. A 1.00 g aliquot of the anhydride-modified polyolefin or anhydride-modified styrene block copolymer is heated to reflux as a solution in water-saturated xylene. To the hot solution are added 3-4 drops of 1% thymol blue in DMF as an indicator and a known excess of 0.05 N ethanolic KOH, e.g., to obtain the blue endpoint of the indicator. The remaining excess KOH is back-titrated with 0.05 N isopropanolic HCl to the yellow endpoint of the indicator. The weight percent of anhydrous moieties relative to the weight of the aliquot analyzed is: The following formula:

number

[0031] To determine the anhydrous moiety content of the total dry mass of the composition of the present invention, it is necessary to first convert the isocyanate groups present to other groups that do not interfere with the determination of the anhydrous moiety. This can be conveniently accomplished by first reacting the composition with benzoic acid in a dry xylene solution under reflux in an excess of 2 to 10 moles per mole of estimated isocyanate content by dry mass. The isocyanate is irreversibly converted to benzamide with the loss of one CO molecule per isocyanate group. The anhydride present in the dry material does not react with or denature the mixed anhydride containing the benzoyl moiety, so the total amount of anhydrous moieties (-C(O)-O-(O)-C-) remains unchanged. After the reaction, the mixture can be evaporated to dryness to recapture the dry mass.

[0032] The determination of anhydrous moieties in the dry mass must be performed in the presence of free carboxylic acid (benzoic acid or other free carboxylic acid released by the above-described anhydrous modification with benzoic acid). This can be done by a method similar to that described in Non-Patent Document 3. A 1.00 g aliquot containing the dry mass of anhydrous moieties is heated to reflux in solution in dry xylene with an accurately measured excess of aniline, 2 to 20 moles per mole of estimated anhydrous moieties in the aliquot. The aniline reacts with the anhydrous moieties but not significantly with the free carboxylic acid groups. The solution is cooled to room temperature, and the remaining excess free aniline is back-titrated with 0.05 N isopropanol HCl to the red endpoint of thymol blue in DMF as indicator. The same amount of aniline used above is directly titrated with HCl under the same conditions as above. The weight percent anhydrous moieties relative to the weight of the analytical aliquot is calculated using the following formula:

number

[0033] The % by weight content of anhydrous parts per gram of the total composition (and thus including any solvents and other optional ingredients) is obtained by accurately weighing an aliquot of the total composition, evaporating the aliquot to dryness at elevated temperature and / or under vacuum, re-weighing the dry aliquot to obtain the dry mass content of the composition, carrying out the above-described conversion of isocyanates to amides with benzoic acid, analyzing the dry mass for anhydrous content, and correcting the obtained dry mass for anhydrous parts by the dry matter content of the total composition.

[0034] The content of anhydrous moieties (as -C(O)-O-(O) moieties) in the entire composition (including the solvent) determined by the above formula 1 is preferably 5 x 10 per gram of the entire composition. -4 Molar ~ 5 x 10 -3 molar range, more preferably 6 x 10 -4 Molar ~ 3 x 10 -3 The content of the anhydrous moiety (—C(O)—O—(O)—C—) relative to the dry mass of the composition (excluding the solvent), as determined by the above formula 2, is preferably in the range of 5×10 per gram of dry mass of the composition. -3 Molar ~ 5 x 10 -2 molar range, more preferably 5 x 10 -3 From 2 x 10 -2 It is in the molar range.

[0035] The weight ratio of the isocyanate-containing crosslinking agent to the sum of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer is preferably in the range of 0.2:1 to 0.8:1 in both the compositions and combinations of the present invention.

[0036] The composition of the present invention is preferably in the form of a solution or dispersion, more preferably in the form of a solution in a solvent.

[0037] On the other hand, the solvent is preferably a compound represented by the following formula: [ka] [In the formula, R 1 and R 2are each independently selected from the group consisting of methyl, ethyl, and branched or straight chain C3-C4 alkyl, with the proviso that R 1 and R 2 the total number of carbon atoms in the range of 4 to 7; or R 1 and R 2 are linked together to form a bridged alkylene -(CH2) m - (wherein m is an integer ranging from 4 to 7). More preferably, the first component comprises one or more aliphatic C5-C8 ketones represented by the formula 1 and R 2 are linked together to form a bridging alkylene -(CH2) m - (wherein m is an integer ranging from 5 to 6). Most preferably, the ketone solvent is essentially (meaning 95% or more by volume, relative to the ketone solvent) cyclohexanone.

[0038] The solvent preferably contains a ketone solvent and a C6-C8-alkane solvent as a second component. The C6-C8-alkane solvent is preferably one or more methyl-substituted cycloalkanes, each of which preferably has a boiling point in the range of 80°C to 130°C, and more preferably in the range of 90°C to 120°C. When the C6-C8-alkane solvent is a mixture of multiple C6-C8-alkanes, the mixture preferably has a boiling point range entirely within the temperature range of 90°C to 140°C, and more preferably within the temperature range of 100°C to 130°C. More preferred examples of C6-C8-alkanes are selected from the group consisting of methylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, and 1,4-dimethylcyclohexane. Most preferably, the C6-C8-alkane solvent is essentially (meaning 95% or more by volume of the C6-C8-alkane solvent) methylcyclohexane.

[0039] Alternatively, the solvent may contain an alkylbenzene solvent as a second component in addition to the ketone solvent. The alkylbenzene solvent is one or more alkylbenzenes, each preferably having a boiling point in the range of 110°C to 170°C, more preferably in the range of 130°C to 150°C. When the alkylbenzene solvent is a mixture of multiple alkylbenzenes, the mixture preferably has a boiling point range entirely within the temperature range of 110°C to 170°C, more preferably entirely within the temperature range of 130°C to 150°C. More preferred examples of alkylbenzenes include mono- to tri-(C1-C3-alkyl)benzenes, even more preferred are mono- to di-(C1-C2-alkyl)benzenes (provided they satisfy the required boiling point or boiling point range), and even more preferred are selected from the group consisting of o-, m-, and p-xylene, and ethylbenzene. The most preferred alkylbenzene solvent is a mixture of xylene and ethylbenzene, particularly a mixture of xylene and ethylene in a weight ratio of 3:1 to 2:1.

[0040] The solvent preferably comprises essentially, i.e., 95% by volume or more, a ketone solvent as a first component, and a C6-C8-alkane solvent (or alkylbenzene solvent) as a second component. These preferred solvents more preferably have the following additional characteristics: a) The boiling point of each of the one or more ketones is 40° C. to 70° C., preferably 50° C. to 60° C. higher than the boiling point of the one or more C6-C8-alkanes. b) The boiling point of each of the one or more ketones is 10°C to 30°C, preferably 15°C to 25°C, higher than the upper boundary of the boiling range of the mixture of alkylbenzenes. c) The weight ratio of alkylbenzene to ketone is in the range of 10:1 to 3:1. d) C6-C8-alkane solvents (or alkylbenzene solvents) do not form azeotropes with any ketones.

[0041] Most preferred is the composition of the present invention in the form of a solution; the composition contains an anhydride-modified polyolefin and an anhydride-modified styrene block copolymer in a total amount ranging from 7 to 18% by weight, based on the entire composition, and the weight ratio of the anhydride-modified polyolefin to the anhydride-modified styrene block copolymer is ranging from 2:1 to 6:1; the composition contains an isocyanate-containing crosslinker in a weight ratio ranging from 0.1:1 to 0.4:1, based on the total amount of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer; and the solvent is a mixture of an alkyl solvent (particularly methylcyclohexane) and a ketone solvent (particularly cyclohexanone), where the weight ratio of the alkyl solvent to the ketone solvent is ranging from 15:1 to 30:1.

[0042] Secondly, the most preferred is the composition of the present invention in the form of a solution; the composition contains an anhydride-modified polyolefin and an anhydride-modified styrene block copolymer in a total amount of 7 to 11 wt % based on the whole composition, and the weight ratio of the anhydride-modified polyolefin to the anhydride-modified styrene block copolymer is in the range of 2:1 to 6:1; the composition is prepared by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst, and then reacting the resulting homogeneous aniline-formaldehyde adduct mixture with phosgene to convert aromatic amine groups to isocyanates. The composition contains an isocyanate-containing crosslinking agent, which is a reaction product obtained by converting an anhydrous styrene-modified polyolefin into an olefin group, in a weight ratio of 0.1:1 to 0.4:1 relative to the total of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer, and the composition is dissolved in a mixture of an alkylbenzene solvent and a ketone solvent (wherein the weight ratio of the alkylbenzene solvent (particularly a mixture of xylene and ethylbenzene in a weight ratio of 3:1 to 2:1) to the ketone solvent (particularly cyclohexanone) is in the range of 6:1 to 3:1).

[0043] The compositions of the present invention have a significantly lower viscosity, which allows them to be applied in liquid form using conventional applicators for liquids, such as doctor blades, kiss coaters, or knife-on-air applicators.

[0044] Furthermore, the compositions of the invention exhibit thixotropic behavior. The term "thixotropy" is understood as the following two properties:

[0045] a) Initial viscosity (before shearing) and final viscosity (shear rate 50 s -1 From the 300s -1 and then increase it to 50s again. -1 a high ratio of shear back to the original; and b) Shear rate is increased to 50 s -1 From the 300s -1 The area under the shear rate-dependent shear stress (Pa) curve when the shear rate was increased to 50 s -1 The mathematical difference between the area under the shear rate dependent shear stress curve when the viscosity is returned to the shear rate. This difference in area is commonly designated in the art as "viscosity hysteresis."

[0046] For purposes of the present invention, the viscosity hysteresis can be approximately calculated as the sum using the following equation (3):

number

[0047] The thixotropic behavior is desirable when applying the composition to a first or second surface. If the composition is allowed to stand for a period of time, such as in a storage container, it may become highly viscous or develop a gel-like viscosity. If the composition in the container is stirred under high shear, the composition will transform into a low-viscosity liquid. Because the composition of the present invention has thixotropic properties, as described above, it will not immediately re-gel once stirring in the container is stopped, but will remain liquid for a certain period of time. After applying the composition to the first and / or second surface and allowing it to stand, the composition of the present invention may be allowed to stand again for a period of time to allow it to re-thicken on the first and / or second surface. This allows the first and / or second pieces to be further processed without risk of losing the composition due to dripping. A high viscosity of the composition after application is desirable, especially when the second portion is in the form of a fabric, where undesirable penetration or spillage of the composition into the fabric mesh may occur if the viscosity of the composition after application is too low.

[0048] The compositions of the invention are preferably devoid of halogens and halogen-containing compounds, i.e., contain less than 0.1% by weight, preferably less than 0.05% by weight, relative to the dry content of the composition, said content being determinable by CHNX elemental analysis.

[0049] The compositions and combinations of the present invention are particularly suitable as adhesion primers for the following material pairs: TPO / polyester, TPO / TPU, and TPO / PU.

[0050] A typical combination is: The first part is made of TPO and the second part is made of TPU, polyester, or PU; A first coating of TPO and a second part made of TPU, polyester, or PU; and First part of TPO and second coating of TPU, polyester, or PU is.

[0051] More preferred combinations to be bonded together are TPO sheet / polyester sheet, TPO sheet / bare (unimpregnated) polyester woven or nonwoven fabric, TPO sheet / TPU-impregnated polyester woven or nonwoven fabric, TPO sheet / TPU sheet, TPO sheet / PU sheet, or TPO sheet / PU coating layer. Particularly preferred material pairs are TPO sheet / bare (unimpregnated) polyester, and TPO / TPU-impregnated polyester woven or nonwoven fabric.

[0052] The TPO of the first part or coating can be purely aliphatic, mixed aliphatic / aromatic, or purely aromatic. Preferably, the TPO is purely aliphatic.

[0053] Most preferably, the TPO is purely aliphatic and selected from: Ethylene homopolymers, i.e. polymers having less than 0.5 mol %, preferably less than 0.1 mol %, of repeat units other than -CH-CH-, relative to the total number of -CH-CH- repeat units, provided that this content is 1 Quantified by H-NMR; Propylene homopolymers, i.e. polymers having less than 0.5 mol %, preferably less than 0.1 mol %, of repeat units other than -CH(CH3)CH2-, relative to the total number of -CH(CH3)CH2- repeat units, provided that this content is 1Measured by H-NMR; Ethene / propene copolymer; ethene / α-olefin copolymers, wherein the α-olefin may be selected from the group consisting of propene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene; Block copolymers containing polyethylene and / or polypropylene hard segments and ethene / propene rubber or non-crosslinked ethene / propene / butadiene rubber soft segments; and Blends of polyethylene and / or polypropylene and ethene / propene rubber and / or non-crosslinked ethene / propene / butadiene rubber.

[0054] The first TPO portion is more preferably a sheet-like material having a planar first surface, in which case the critical first surface energy of the first surface of the sheet-like TPO material at 25°C is preferably in the range of 28 to 38 millinewtons / meter (mN / m), more preferably in the range of 30 to 38 mN / m.

[0055] For purposes of the present invention, the critical first surface energy of the planar TPO first surface can be determined using a Zisman plot, where the known first surface tensions γL (x-axis) of a set of test solvents are plotted against the cosine of their observed contact angles (y-axis) with the TPO surface under test, measured by the sessile drop (static) method at 25°C, and the selected set of (x / y) measurement points are fitted with a linear regression line to obtain the critical surface energy of the TPO surface under test as the x-value at the intersection of the linear regression line with a horizontal line y = 1.0 (cosine of the contact angle = 1.0, i.e., contact angle = 0). The set of test solvents, which are formaldehyde (FM) or a mixture of ethylene glycol (EG) and 2-ethoxyethanol (EE), are shown in Table 1 below: [Table 1] However, in the Zisman plot, only test solvents in Table 1 that have a contact angle with the TPO surface to be tested that is greater than 0 (the test solvent does not spread on the TPO surface) can be used. The test settings and conditions for measuring the contact angle can be, for example, those described in Non-Patent Document 4.

[0056] The first TPO part typically has a planar first surface having a critical first surface tension in the preferred ranges described above, which does not require any pretreatment of the first surface, such as plasma treatment, or autoxidation in air or air / ozone, and / or sunlight, for the methods and compositions of the present invention, although such pretreatment of the first surface may optionally be performed to further enhance adhesion between the composition and the second part.

[0057] The first TPO coating is typically produced by melt coating or extrusion coating onto the second part using an extrusion coating die, etc. Such in situ formed TPO coatings automatically have a critical first surface tension in the preferred range at the interface with the second part, since the interface is formed in situ by molten, untreated TPO that may not have yet come into contact with atmospheric light or oxygen.

[0058] The polyester for the second portion or coating can generally be any synthetic polyester known in the art. For purposes of this invention, polyester soft segments within the scope of the TPU description can be similar to the following: a diol reacted with a dicarboxylic acid, or more conveniently, a diol reacted with the dimethyl ester of a dicarboxylic acid (transesterification) and boiled in low-boiling methanol. The diol for the polyester is an aliphatic linear or branched C2-C8 diol, optionally containing a saturated C5-C6 carbocyclic ring. Examples of such diols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 2-methylpropanediol, 3-methylpentane-1,5-diol, 1,6-hexanediol, or cyclohexanedimethanol, and mixtures of these diols. The dicarboxylic acid for the polyester diol is an aliphatic linear or branched C2-C8 dicarboxylic acid. Examples of such dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid, or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, or dimethyl terephthalate, or mixtures thereof. The polyester may be end-capped with a diol end or, optionally, with suitable etherified, esterified, carbonate-forming, or urethane-forming end groups. More preferably, the polyester is PBT (polybutylene terephthalate), PET (polyethylene terephthalate), PTT (polytrimethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), PEC (polyestercarbonate), or PAR (aromatic polyester).

[0059] The TPU for the second part or coating can generally be obtained from the reaction of a diisocyanate-containing hard block segment with a polyester diol soft block segment, and the molar ratio of isocyanate groups to isocyanate-reactive hydroxy groups present in the reaction mixture is "N NCO " / "N OH" is 0.9 to 1.1, more preferably 0.95 to 1.05, and most preferably 0.99 to 1.01. In the above ratio, N NCO is the number of isocyanate groups in the mixture, which can be obtained by titration with an amine followed by back-titration of the excess amine with a standard acid, expressed in mmol of isocyanate groups per gram of dry (or pure, solvent-free) weight of the mixture, N OHis the hydroxyl number of the mixture of compounds, expressed in mmol of hydroxyl groups per gram of dry (or pure, solvent-free) weight of the mixture. Diisocyanate-containing hard blocks can be obtained by the reaction of a diisocyanate with a diol chain extender. The diisocyanate can be a pure compound or a mixture of diisocyanates. In one preferred embodiment, the diisocyanate is an aromatic diisocyanate, more preferably 2,2'-, 2,4'-, or preferably 4,4'-diphenylmethane diisocyanate. Suitable diol chain extenders include aliphatic C2-C6 diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, 2-methylpropanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,2-hexanediol, and 3-methylpentane-1,5-diol; glycol ethers such as diethylene glycol, dipropylene glycol, and tripropylene glycol; and amino alcohols such as ethanolamine and N-methyldiethanolamine. The polyester diol soft segment used preferably has a molecular weight of 500 to 20,000. These can be prepared by reacting a diol with a dicarboxylic acid, or more conveniently, by reacting a diol with the dimethyl ester of the dicarboxylic acid (transesterification) and evaporating the low-boiling methanol. The diols for the polyester diols are aliphatic linear or branched C2-C8 diols that may contain saturated C5-C6 rings. Examples include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 2-methylpropanediol, 3-methylpentane-1,5-diol, 1,6-hexanediol, or cyclohexanedimethanol, and mixtures of these diols. The dicarboxylic acids for the polyester diols are aliphatic linear or branched C2-C8 dicarboxylic acids.Examples of these include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid, or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, or dimethyl terephthalate, or mixtures thereof.

[0060] The PU for the second coating is a polyurethane containing at least weak crosslinking. These PU coatings can be obtained from crosslinkable TPUs, which may already be partially self-crosslinked, made from a mixture of di-, tri-, and / or polyisocyanates and polymeric diols. The di-, tri-, or polyisocyanates are typically one of the isocyanate-containing crosslinkers listed above. The polymeric diol can also be a dihydroxy-endcapped TPU, which can be obtained from TPUs, as described for the second TPU, by blocking both ends with hydroxy groups using a suitable diol, as listed above in the preparation of the TPU itself. Alternatively, the polymeric diol may be a polyester diol (prepared by, for example, the condensation polymerization of 1,2-dihydroxyethane, 1,2- or 1,3-dihydroxypropane, 1,2-, 1,3-, or 1,4-dihydroxybutane, and / or 1,6-dihydroxyhexane with adipic acid), a polyether diol (prepared by, for example, the ring-opening polymerization of oxirane, 1,2-epoxypropane, 1,2-epoxybutane, or tetrahydrofuran), a polycaprolactone diol (prepared by the ring-opening polymerization of ε-caprolactone), or a polycarbonate diol (prepared by, for example, the condensation polymerization of a diol with dimethyl or diethyl carbonate, as exemplified above for the polyester diol). The pre-reaction is carried out in a mixing ratio of polyisocyanate and polyol such that there is a molar excess of isocyanate moieties relative to hydroxy moieties (usually present in excess in the prepolymer after completion of the pre-reaction). Optionally, a chain extender such as 1,4-butanediol is used in the preparation of the crosslinkable TPU. The crosslinkable TPU made from diisocyanate and polymeric diol is preferably used in the form of a solution in a suitable solvent, such as an ester solvent, particularly ethyl acetate or butyl acetate, optionally mixed with acetone. It is mixed with a crosslinking agent capable of reacting with functional groups present in the crosslinkable TPU, such as hydroxy, ester, carboxyl, amide, or urethane, prior to use.Examples of such crosslinkers include diisocyanates (such as those exemplified above in Alternative ii) of the isocyanate-containing crosslinker), carbodiimides, or aziridines. Crosslinking / curing begins after mixing the crosslinkable TPU with the crosslinker.

[0061] The first portion or coating has a first surface with a first predetermined area, and the second portion or coating has a second surface with a second predetermined area. In the case of sheet-like first and / or second portions, the first and / or second areas are typically the geometric areas of the top and / or bottom of the sheet-like first and / or second portions. In the case of first and / or second portions that cannot be precisely defined geometrically, such as fibers, the first and / or second surfaces typically have first and / or second areas calculated as the quotient (first surface) of the "weight of the first portion" divided by the "weight per unit area of ​​the first portion" or the quotient (second surface) of the "weight of the second portion" divided by the "weight per unit area of ​​the second portion."

[0062] The composition of the present invention may be in a pure, solvent-free form. The composition may be in the form of a solvent-free liquid, powder, or solution, depending on the melting points of the components and the application temperature. The composition of the present invention is preferably applied in the form of a solution, dispersion, or suspension in the solvent described above. A composition of the present invention in the form of a dispersion or suspension can be obtained, for example, by first dissolving the composition of the present invention in a solvent in which the components are essentially insoluble at room temperature, heating and optionally sonicating to form a heated solution, and then cooling the solution to room temperature, optionally with stirring or sonication, to precipitate the solid and / or liquid components from the solvent as finely dispersed solid particles and / or droplets. When the anhydride-modified polyolefin, the anhydride-modified styrene block copolymer, and the isocyanate-containing crosslinking agent are all solid at room temperature, the composition of the present invention in the form of a dispersion or suspension can also be prepared by micronizing the anhydride-modified polyolefin, the anhydride-modified styrene block copolymer, and the isocyanate-containing crosslinking agent and suspending the resulting microparticles in a solvent. It is understood that compositions in which the anhydride-modified polyolefin, the anhydride-modified styrene block copolymer, and the isocyanate-containing crosslinker are partially dissolved and partially dispersed (as particles and / or as droplets), depending on their solubility in the solvent, can also be used for purposes of the present invention.

[0063] When the composition is in the form of a solution, suspension, or dispersion in a solvent, the total solids content of the solution, suspension, or dispersion is preferably 5 to 25% by weight, more preferably 8 to 25% by weight, based on the composition.

[0064] It is understood that the anhydride-modified polyolefin, the anhydride-modified styrene block copolymer, and the isocyanate-containing crosslinker can be used in unmixed form, separately, sequentially, or simultaneously, provided that all three are applied as a composite and in amounts appropriate for the purposes of the present invention. The order in which the anhydride-modified polyolefin, the anhydride-modified styrene block copolymer, and the isocyanate-containing crosslinker are applied is not critical. Each of these may be applied by itself in a solvent-free form, such as in a molten or particulate form, or may be applied as a solution in a solvent such as those exemplified above for the overall composition of the present invention, although this is not required. Each individual component can be applied as a solution in a solvent specifically suited to that particular component. Examples of such individual solvents include ethers, esters (e.g., ethyl acetate), ketones, halogenated hydrocarbons, aliphatic or aromatic hydrocarbons, amides (e.g., DMF), glycol ethers, DMSO, or acetonitrile, or mixtures of these solvents. The solvent must be removable by evaporation under drying conditions similar to those for the overall composition of the present invention in solution or dispersion form.

[0065] In the process of the present invention, the composition or combination of the present invention is preferably applied to the first and / or second surface in a dry mass of 10 to 40 g per square meter of total area of ​​the first and / or second surface, i.e., this amount may be applied completely to the first surface (e.g., if the second coating is applied to the first surface of the first part), or to the second surface (e.g., if the first coating is applied to the second surface of the second part), or may be applied partially to the first surface and the remainder to the second surface (e.g., if the first surface of the first part is attached to the second surface of the second part).

[0066] If both the first and second parts are actually bonded parts (neither is coated), the composition or combination of the present invention may be applied to either the first surface of the first part, or the second surface of the second part, or may be applied to both the first and second surfaces. If the second part is a woven or nonwoven fabric, the composition or combination of the present invention is preferably adhered to said second part so that the fabric can absorb some amount of the composition or combination of the present invention at or near the second surface. This allows for a process step of laminating the composition or combination of the present invention to the first part, and a process step of bonding the first and second parts using heat and pressure. process can be held for a period of time.

[0067] If a first part is coated with a second coating, the composition or combination of the present invention is typically applied to a first surface of the first part. Alternatively, if a second part is coated with a first coating, the composition or combination of the present invention is typically applied to a second surface of the second part.

[0068] Application of the compositions and combinations of the present invention can be carried out by any of the techniques conventionally used in the art for applying liquid, molten, or powder compositions, including kiss coating, spray coating, doctor blade, powder dusting, and coating by electrostatic powder coating.

[0069] Drying of the composition or combination once applied to the first and / or second portions can typically be carried out at a temperature of from 50° C. to 130° C. for a time sufficient to remove the solvent.

[0070] When the first and second parts (neither coated) are bonded together, heating during bonding is preferably performed to a maximum temperature 20°C to 50°C higher, more preferably 30°C to 40°C higher, than the melting point of the TPO in the first part. The melting point of TPO was determined by differential scanning calorimetry (DSC) according to ISO standard 11357-3. The maximum temperature is preferably maintained for 1 to 5 minutes, provided that the time is sufficient for the layers of the three components to promote adhesion between the first and second surfaces. Heating is preferably performed without the use of steam. Heating is preferably performed under ambient conditions (e.g., air) or, optionally, in an inert gas such as nitrogen. Heating of the first and second surfaces can be performed by inserting the first and second parts and / or coatings into a hot press or oven. If pressure is applied during heating, the pressure can be 5 to 30 bar, preferably 15 to 25 bar, above atmospheric pressure.

[0071] Alternatively, if a first melt coating of TPO is applied to a second part (such as polyester or TPU), heating may be performed by applying the TPO in molten form onto the second part. Such application is typically performed using an extruder (extrusion-then melt coating). The extrusion temperature is preferably 60°C to 120°C, more preferably 70°C to 110°C, higher than the melting point of the TPO being extruded. The extruded first TPU coating is then melt-coated onto the second part, for example, using a calender roll heated to a temperature typically between 50°C and 80°C.

[0072] As a further alternative, if a first portion of TPO is to be adhered to a second coating of crosslinked PU, the crosslinkable PU can be first applied to the first TPO portion, optionally in the form of a suitable solvent, followed by solvent drying, followed by the same procedure as set out above for adhering the first and actual second portions, except that the maximum heating temperature selected will be sufficient to crosslink the applied crosslinkable coating.

[0073] Optionally, the compositions and combinations of the present invention may contain antistatic or conductive additives. This is preferred because the pair of materials bonded together by the compositions or combinations of the present invention have very high electrical resistance. The antistatic or conductive additive may be any conventional additive used in the field of automotive paints, as described in the introduction. Examples of additives may be selected from the group consisting of carbon black, soot, conductive (nitrogen-doped) titanium dioxide, conductive (aluminum-doped) zinc dioxide, conductive (antimony-doped) tin oxide, and conductive (antimony-doped) indium oxide.

[0074] The invention is illustrated by the following non-limiting examples.

[0075] Example 1: Formulation of a composition in solution form

[0076] The formulations are shown in Table 2 below, where all amounts are in weight percent of the total composition unless otherwise specified. The weight ratio of anhydride-modified polyolefin to anhydride-modified styrene block copolymer is 4:1 in all formulations.

[0077] [Table 2]

[0078] Comparative Example 2 and Examples 3-7: Adhesion test of the solution-form composition of the present invention for a pair of TPO sheet and PET fabric

[0079] Adhesion tests were conducted on TPO sheets adhered to sheets of PET spunbond fabric or sheets of PET woven fabric. The properties of the TPO sheet (TPO1) and two types of PET fabric (PET-spun, and PET-multiPET-multi) are shown in Tables 3 and 4 below, respectively.

[0080] [Table 3]

[0081] [Table 4]

[0082] The compositions of the present invention, when present, were applied to PET substrates using a Zehmtner GmbH 2000 Universal Applicator lab film coater (Comparative Example 2) or a Mathis AG LTE-S doctor blade coater (Examples 3-7). Each composition-coated substrate was dried at 100°C for 3 hours in the LTE-S lab coater. Each substrate was stacked with two foils of TPO1 with a total thickness of 0.45 mm to form layered composites with the following structure: |substrate|(composition or combination of the present invention)|TPO1|TPO1|(composition or combination of the present invention)|substrate|. This double lamination was performed to obtain a central TPO1 monolayer of sufficient thickness after hot pressing. Each of these double-laminate composites was inserted between the metal plates of a Schwabenthan Polystat 400 press, using 1.2 mm-thick metal spacers between each metal plate and the adjacent substrate layer. Teflon layers were also applied between the composites and each metal plate to prevent sticking. Each double laminate composite was heat treated in a lab press and simultaneously pressed at 20 bar. The remaining processing parameters for application of the compositions, i.e., dry mass per square meter of surface after drying of the applied compositions (i.e., the combinations of the present invention), heat treatment parameters, and the thickness and peel strength results of the final layered composites are shown in Table 5 below.

[0083] Peel strength values ​​were measured using a "Zwick Roell 20 KN Allround table-top" testing machine. The test samples were 20 mm wide and at least 250 mm long, and the test speed was 100 mm / min. The force required to peel the fabric from the thermoplastic foil and the travel were recorded on the device. For recording purposes, the starting area, i.e., the first 10 mm, was not used. The minimum area is the average value over the detection area. The test result [N / cm] is the separation force over a 1 cm width according to the DIN 53530 standard.

[0084] [Table 5]

[0085] The above results demonstrate that the layered composites of Examples 3-7 of the present invention all exhibited superior peel strength to the layered composite of Comparative Example 2. In other words, the use of a composition or combination of the present invention as an adhesion promoter on the second part in the form of a polyester woven fabric can enhance the adhesion of TPO to the first part. The above results also demonstrate that coating the second part in the form of a woven fabric with a doctor blade (Examples 4-7) does not result in soaking of the fabric with the composition, whereas coating the same composition with a film coater (Example 3) does. Soaking is undesirable because it reduces the amount of composition available at the interface between the first surface of the TPO sheet and the second surface of the polyester woven fabric. The results also demonstrate that applying a small amount of the composition of the present invention in a single doctor blade run and heating it to a maximum temperature approximately 35°C higher than the DSC melting point of TPO1 (see Table 3) provides the best peel strength (layered composite of Example 7). Applying more composition with two or more doctor blade runs results in a small decrease in peel strength under otherwise identical conditions (layered composite of Example 7 vs. layered composite of Example 5). Heating to a maximum temperature only about 10°C above the DSC melting point of TPO1 results in a significant decrease in peel strength. This decrease can only be partially offset by using significantly more composition, thereby requiring more doctor blade runs to apply the composition (layered composite of Example 7 vs. layered composites of Examples 6 and 4).

[0086] Comparative Examples 8, 10, 13, 18-19, and 20-23, and Examples 9, 11-12, 14-17, and 24-27: Adhesion Tests of Melt-Coated TPO and PET Fabric Pairs Using the Compositions of the Invention

[0087] The TPO used was TPO2 in all cases, and the substrate was either PET-spun or PET-multi, as described in Tables 3 and 4 above. The inventive composition, if present, was applied to the PET substrate by a knife on the air system of a Coatema Line Coater, followed by drying in a lab coater at 120°C to 130°C for 3 minutes. The TPO was then applied by melt coating using an extrusion coating die. Peel strength measurements of the final composite were performed as described in Comparative Example 2 and Examples 3-7 above, whereby peeling of the top substrate from the remainder of the layered compound was measured as described in Comparative Example 2 and Examples 3-7 above. The composition type (if present), melt-coated TPO and substrate type, and measured peel strengths are listed in Table 6 below.

[0088] [Table 6]

[0089] The above results show that: a) When the composition of the present invention is used as a primer for bonding PET and TPO, it is necessary to include a certain amount of an isocyanate-containing crosslinker (e.g., in the range of 1% to 8% by weight, preferably 2% to 6% by weight, based on the total weight of the composition) to enhance the peel strength obtained by simple mechanical bonding between PET and TPO using spunbonded PET fibers (Examples 11 and 12 vs. Comparative Example 8). If the isocyanate-containing crosslinker is not present in the composition, insufficient peel strength is obtained (Comparative Example 10). b) The compositions of the present invention are clearly superior as primers for bonding PET and TPO to reference primer compositions containing a combination of an isocyanate-containing crosslinker and a crosslinkable polyurethane (Examples 11, 12, 14-17, 24-27 vs. Comparative Examples 20 and 21). The compositions of the two comparative examples lack any significant primer effectiveness. c) A composition of the present invention having the following characteristics: The total content of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer is preferably in the range of 7% by weight to 11% by weight based on the total weight of the composition; The weight ratio of the anhydride-modified styrene block copolymer to the anhydride-modified polyolefin is preferably in the range of 2:1 to 6:1; the amount of isocyanate-containing crosslinker is in the range of 1% to 8% by weight of the composition, or the isocyanate-containing crosslinker is present in a weight ratio of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer in the range of 20:1 to 30:1; and The composition is in the form of a solution in a mixture of an alkyl solvent and a ketone solvent, and the volume ratio of the alkyl solvent to the ketone solvent in the mixture is preferably in the range of 20:1 to 30:1; is considered to be the first and most preferred embodiment for bonding PET and TPO (Examples 11 and 12). d) A composition of the present invention having the following characteristics: The total content of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer is preferably in the range of 7% by weight to 11% by weight based on the total weight of the composition; Isocyanate-containing crosslinkers prepared by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst to convert aromatic amino groups into isocyanate groups, and then reacting the resulting homogeneous aniline-formaldehyde adduct mixture with phosgene; the amount of the isocyanate-containing crosslinker is in the range of 1% to 8% by weight based on the total composition, or preferably in a weight ratio based on the total of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer in the range of 0.2:1 to 0.4:1; and The composition is in the form of a solution in a mixture of an alkylbenzene solvent and a ketone solvent, and the volume ratio of the alkylbenzene solvent to the ketone solvent in the mixture is preferably in the range of 6:1 to 3:1; is considered to be the second most preferred embodiment for bonding PET and TPO (Example 26).

[0090] Therefore, the triple combination of an anhydride-modified polyolefin, an anhydride-modified styrene block copolymer, and an isocyanate-containing crosslinker of the present invention is believed to have a synergistic effect on peel strength greater than the dual combinations of an anhydride-modified polyolefin and an anhydride-modified styrene block copolymer, and the dual combination of an isocyanate-containing crosslinker and a crosslinkable TPU.

[0091] Example 27: Adhesion of a crosslinked PU coating on a TPO top layer of a conveyor belt

[0092] The compositions of the present invention were applied to the TPO layer of a commercially available conveyor belt (models CNB-8E or CNB-6EB-A1, marketed by the applicant, containing a wear improver that weakens the adhesion of the primer of the present invention) in the same manner as in formulations 1, 3-8, or 11-14 in Table 2, followed by drying at 100°C for 5 minutes. A commercially available solvent-based crosslinkable PU was applied on top of the dried layer of the inventive combination and dried under the same conditions as the application and drying of the inventive composition. The above solvent-based crosslinkable PU was also applied to the TPO layer of a reference sample of the same type of conveyor belt under the same conditions, except that it was not previously coated with the inventive composition. In the crosslinkable PU-coated reference conveyor belt, the PU coating could be manually separated from the TPO layer; i.e., the crosslinkable PU coating did not adhere to the TPO layer. In contrast, PU coated conveyor belts containing pre-coated materials with the inventive combination were able to undergo dynamic testing on a De Mattia Flexon Check instrument from Gibitre Instruments for 1 million cycles (flexion and reverse flexion), during which the crosslinked PU coating did not peel off from the TPO layer and no cracks occurred. The disclosure of this specification may include the following aspects. (Aspect 1) 1. A composition in the form of a solution or dispersion in a solvent, comprising: Anhydrous modified polyolefin, an anhydride-modified styrene block copolymer, and Isocyanate-containing crosslinking agents The anhydride-modified polyolefin and the anhydride-modified styrene block copolymer are present in a total amount ranging from 7% by weight to 18% by weight based on the total weight of the composition; the weight ratio of the anhydride-modified polyolefin to the anhydride-modified styrene block copolymer is in the range of 2:1 to 6:1; the weight ratio of the isocyanate-containing crosslinker to the sum of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer is in the range of 0.2:1 to 0.5:1; The solvent comprises, as a first component, a compound having the following formula:

change

Claims

1. 1. A composition in the form of a solution or dispersion in a solvent, comprising: Anhydrous modified polyolefin, an anhydride-modified styrene block copolymer, and Isocyanate-containing crosslinking agents The anhydride-modified polyolefin and the anhydride-modified styrene block copolymer are present in a total amount ranging from 7% by weight to 18% by weight based on the total weight of the composition; the weight ratio of the anhydride-modified polyolefin to the anhydride-modified styrene block copolymer is in the range of 2:1 to 6:1; The solvent has as a first component a compound represented by the following formula: 【Chemistry 1】 [In the formula, R １ and R ２ are each independently methyl, ethyl, and branched or linear C ３ -C ４ alkyl, with the proviso that R １ and R ２ the total carbon number of R ranges from 4 to 7; or １ and R ２ is bonded to -(CH ２ ) ｍ - (wherein m is an integer of 4 to 7). One or more aliphatic C ５ -C ８ and a second component, C, containing a ketone solvent, which is a ketone. ６ -C ８ 1. Use of a composition for promoting adhesion of a TPO to a polyester, the composition comprising an alkane solvent, the isocyanate-containing crosslinker has an NCO content of 10 to 35 wt. % based on the isocyanate-containing crosslinker, measured according to DIN Standard 11909 (2007) at room temperature, and the composition comprises the isocyanate-containing crosslinker in a peel strength-enhancing amount of 2 to 6 wt. % based on the total composition; the weight ratio of the isocyanate-containing crosslinking agent to the total of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer in the composition is 0.2:1 to 0.5:1; use.

2. Anhydrous modified polyolefin (1) A method for producing a polyolefin selected from the group consisting of polyethylene, ethylene-α-olefin copolymers (wherein the α-olefin is selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene), and polypropylene, - Maleic anhydride Diels-Alder reaction products of maleic anhydride with buta-1,3-diene, cyclopentadiene, or cyclohexa-1,3-diene, and - reaction products of maleic anhydride with α-olefins selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene or by grafting with an olefin anhydride selected from the group consisting of (2) The use according to claim 1, which is obtained by copolymerizing an olefin anhydride as defined above with ethylene and / or an α-olefin as defined above.

3. 3. The use according to claim 1 or 2, wherein the styrene block copolymer in the anhydride-modified styrene block copolymer is selected from the group consisting of SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), and SEBS (styrene-(ethylene-co-butylene)-styrene).

4. The isocyanate-containing crosslinking agent (1) A reaction product obtained by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst, followed by reacting the resulting homogeneous aniline-formaldehyde adduct mixture with phosgene; (2) selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, diisophorone diisocyanate, and diphenyl ether-2,4,4-triisocyanate; or (3) Uretidinedione- and / or 2,4,6-trioxotriazine-containing oligomers of 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate The use according to any one of claims 1 to 3, wherein

5. The use according to any one of claims 1 to 4, wherein the first component of the solvent is cyclohexanone and the second component of the solvent is methylcyclohexane.

6. 6. The use according to claim 5, wherein the weight ratio of the methylcyclohexane to the cyclohexanone is in the range of 15:1 to 30:

1.

7. The solvent comprises at least 95% by volume of a ketone solvent as a first component and a C ６ -C ８ The use according to any one of claims 1 to 6, which comprises an alkane solvent.

8. The use according to any one of claims 1 to 7, wherein the TPO is a TPO moiety in the form of a sheet-like material having a planar first surface with a critical first surface energy at 25°C of 28 to 38 mN / m.

9. The anhydride-modified polyolefin, (1) A method for producing a polyolefin selected from the group consisting of polyethylene, ethylene-α-olefin copolymers (wherein the α-olefin is selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene), and polypropylene, - Maleic anhydride Diels-Alder reaction products of maleic anhydride with buta-1,3-diene, cyclopentadiene, or cyclohexa-1,3-diene, and - reaction products of maleic anhydride with α-olefins selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene or by grafting with an olefin anhydride selected from the group consisting of (2) obtained by copolymerizing an olefin anhydride as defined above with ethylene and / or an α-olefin as defined above, or the styrene block copolymer in the anhydride-modified styrene block copolymer is selected from the group consisting of SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), and SEBS (styrene-(ethylene-co-butylene)-styrene); or The isocyanate-containing crosslinking agent (1) A reaction product obtained by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst, followed by reacting the resulting homogeneous aniline-formaldehyde adduct mixture with phosgene; (2) selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, diisophorone diisocyanate, and diphenyl ether-2,4,4-triisocyanate; or (3) Uretidinedione- and / or 2,4,6-trioxotriazine-containing oligomers of 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate That is, 7. Use according to claim 1, 5 or 6.

10. 1. A composition in the form of a solution or dispersion in a solvent, comprising: Anhydrous modified polyolefin, an anhydride-modified styrene block copolymer, and Isocyanate-containing crosslinking agents Including, the isocyanate-containing crosslinker has an NCO content of 10 to 35 wt. % based on the isocyanate-containing crosslinker, measured according to DIN Standard 11909 (2007) at room temperature, and the composition comprises the isocyanate-containing crosslinker in a peel strength-enhancing amount of 2 to 6 wt. % based on the total composition; the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer are present in a combined amount ranging from 7% to 18% by weight based on the total weight of the composition; the weight ratio of the anhydride-modified polyolefin to the anhydride-modified styrene block copolymer is in the range of 2:1 to 6:1; the weight ratio of the isocyanate-containing crosslinker to the sum of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer is in the range of 0.2:1 to 0.5:1; The solvent has as a first component a compound represented by the following formula: 【Chemistry 2】 [In the formula, R １ and R ２ are each independently methyl, ethyl, and branched or linear C ３ -C ４ alkyl, with the proviso that R １ and R ２ the total carbon number of R ranges from 4 to 7; or １ and R ２ is bonded to -(CH ２ ) ｍ - (wherein m is an integer of 4 to 7). One or more aliphatic C ５ -C ８ A composition comprising a ketone solvent, which is a ketone, and as a second component, an alkylbenzene solvent, which is a mixture of xylene and ethylbenzene.

11. Anhydrous modified polyolefin (1) A method for producing a polyolefin selected from the group consisting of polyethylene, ethylene-α-olefin copolymers (wherein the α-olefin is selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene), and polypropylene, - Maleic anhydride Diels-Alder reaction products of maleic anhydride with buta-1,3-diene, cyclopentadiene, or cyclohexa-1,3-diene, and - reaction products of maleic anhydride with α-olefins selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene or by grafting with an olefin anhydride selected from the group consisting of (2) The composition according to claim 10, which is obtained by copolymerizing an olefin anhydride as defined above with ethylene and / or an α-olefin as defined above.

12. 12. The composition of claim 10 or 11, wherein the styrene block copolymer in the anhydride-modified styrene block copolymer is selected from the group consisting of SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), and SEBS (styrene-(ethylene-co-butylene)-styrene).

13. The isocyanate-containing crosslinking agent (1) A reaction product obtained by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst, followed by reacting the resulting homogeneous aniline-formaldehyde adduct mixture with phosgene; (2) selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, diisophorone diisocyanate, and diphenyl ether-2,4,4-triisocyanate; or (3) Uretidinedione- and / or 2,4,6-trioxotriazine-containing oligomers of 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate The composition according to any one of claims 10 to 12, wherein

14. The composition of any one of claims 10 to 13, wherein the first component of the solvent is cyclohexanone.

15. the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer are present in a combined amount ranging from 7% to 11% by weight of the total composition, and the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer are present in a weight ratio ranging from 2:1 to 6:1; the isocyanate-containing crosslinker is a reaction product obtained by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst, and then reacting the resulting homogeneous aniline-formaldehyde adduct mixture with phosgene to convert aromatic amine groups to isocyanate groups, and the isocyanate-containing crosslinker is present in a weight ratio of 0.2:1 to 0.5:1 based on the total weight of the anhydride-modified polyolefin and the anhydride-modified styrene block copolymer; and 15. The composition of claim 14, wherein the alkylbenzene solvent and the ketone solvent are in a weight ratio of 6:1 to 3:

1.

16. 16. The composition of claim 15, wherein the alkylbenzene solvent is a mixture of xylene and ethylbenzene in a weight ratio of 3:1 to 2:

1.

17. The composition of any one of claims 10 to 16, wherein the solvent consists of at least 95% by volume of a ketone solvent as a first component and an alkylbenzene solvent as a second component.

18. Use of a composition according to any one of claims 10 to 17 for promoting the adhesion of TPO to TPU, polyester or PU.

19. The anhydride-modified polyolefin, (1) A method for producing a polyolefin selected from the group consisting of polyethylene, ethylene-α-olefin copolymers (wherein the α-olefin is selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene), and polypropylene, - Maleic anhydride Diels-Alder reaction products of maleic anhydride with buta-1,3-diene, cyclopentadiene, or cyclohexa-1,3-diene, and - reaction products of maleic anhydride with α-olefins selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene or by grafting with an olefin anhydride selected from the group consisting of (2) obtained by copolymerizing an olefin anhydride as defined above with ethylene and / or an α-olefin as defined above, or the styrene block copolymer in the anhydride-modified styrene block copolymer is selected from the group consisting of SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), and SEBS (styrene-(ethylene-co-butylene)-styrene); or The isocyanate-containing crosslinking agent (1) A reaction product obtained by first reacting aniline with formaldehyde in the presence of a hydrochloric acid catalyst, followed by reacting the resulting homogeneous aniline-formaldehyde adduct mixture with phosgene; (2) selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, diisophorone diisocyanate, and diphenyl ether-2,4,4-triisocyanate; or (3) Uretidinedione- and / or 2,4,6-trioxotriazine-containing oligomers of 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate That is, 19. The use according to claim 18.

20. 1. A method for bonding a first surface of a first piece of TPO to a second surface of a second piece of polyester or TPU using heat and, optionally, pressure, comprising the steps of: - applying a composition according to any one of claims 10 to 17 to the first and / or second surface; and Using heat and optionally pressure to bond a first surface coated with the composition to a second surface, or a first surface to a second surface coated with the composition, or a first surface coated with the composition to a second surface coated with the composition. A method comprising:

21. 21. The method of claim 20, wherein during bonding of the first and second surfaces, the first and second surfaces are heated to a temperature 20°C to 50°C higher than the melting point of the TPO of the first part, wherein the melting point is measured by differential scanning calorimetry (DSC) according to ISO standard 11357-3.

22. 18. A method for adhering a first coating of TPO to a second surface of a second piece of polyester or TPU by extrusion and melt coating, comprising the steps of applying a composition according to any one of claims 10 to 17 to the second surface, and extruding and melt coating the TPO onto the combination or composition-coated second surface.

23. 18. A method for adhering a second coating of TPU to a first surface of a first portion of TPO by extrusion and melt coating, comprising the steps of applying a composition according to any one of claims 10 to 17 to the first surface, and extruding and melt coating the TPU onto the composition-coated first surface.

24. 1. A method for bonding a second coating of crosslinked PU to a first surface of a first portion of TPO by applying heat and, optionally, pressure, comprising the steps of: - application of a composition according to any one of claims 10 to 17 to a first surface of a crosslinkable TPU; and - by applying heat and optionally pressure, the crosslinkable TPU is bonded to the first surface coated with the composition, thereby simultaneously crosslinking the crosslinkable PU to form a crosslinked PU. A method comprising:

25. 25. The method of claim 24, wherein the crosslinkable PU is applied as a solution in a solvent and the solvent is evaporated before bonding by applying heat and optionally pressure.

26. 26. The method of any one of claims 20 to 25, wherein the composition is applied to the first surface and / or the second surface at a dry weight of from 10 g to 40 g per square meter of total area of ​​the first surface and / or the second surface.

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