Universal adhesion promoter based on organofunctional modified polybutadiene

Abstract

To provide an adhesion promoter for producing a coating composition and the like, which demonstrates good adhesion to surfaces, and simultaneously allows adjustment of the compatibility according to the underlying surfaces.SOLUTION: A universal adhesion promoter contains a compound based on a polybutadiene, having at least one repeat unit containing a monovalent organic radical or hydrogen radical and a divalent radical of alkyl ether and alkylene alcohol.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a universal adhesion promoter comprising a compound based on organically functionalized polybutadiene. [Background technology]

[0002] Modern materials science is generating an increasing number of composite and hybrid materials, and creating new coating compositions in an accelerating process of innovation. This has created a great demand for innovative adhesion promoters. The goal is to first establish affinity to these same novel surfaces, and at the same time, to have excellent compatibility with the applied coating matrix in order to generate good adhesive bonding to the material. Here, composite materials, hybrid materials, and their surfaces are used as synonyms, while the underlying surface and substrate are used as synonyms.

[0003] Adhesion is primarily due to the bonding force between the molecules of the coating film or coating composition and the underlying surface. If the adhesive strength is insufficient, various methods can be used to address or affect this interface. The surface of the substrate / underlying surface may be modified by sanding, framing, or corona treatment; an additional layer ("adhesion primer") may be introduced between the substrate and the coating film; or adhesion to the coating film may be induced by adding a specific adhesive resin or adhesion promoter.

[0004] Adhesion promoters are components of the coating layer and must, on the one hand, form a strong interaction with the substrate, and in parallel, have a portion that ensures good embedding into the coating matrix without adversely affecting other coating properties.

[0005] Adhesion promoters known in the prior art can be subdivided into functionalized polymers and organic substances, and more broadly into coupling agents. Functionalized polymers include functionalized polyethylene / polypropylene, as well as functionalized styrene-butadiene rubber and organic resins, while functionalized organic substances are essentially amine compounds and acrylates. The group of coupling agents is mainly composed of organically modified silanes, zirconates, and titanates.

[0006] Patent Document 1 describes an adhesive formulation containing acrylate-terminated urethane-polybutadiene that can be prepared from the reaction of a mono-adduct of a reactive olefin compound, diisocyanate, and hydroxy-terminated polybutadiene. Patent Document 2 discloses polybutadiene having terminal epoxy groups, which is used as a binder for adhesive compositions for automotive applications.

[0007] Adhesion promoters composed of unmodified polybutadiene are also known from the prior art. Although they already exhibit good adhesion performance, they have the drawback that their compatibility cannot be adjusted or can only be adjusted within a very limited range. Therefore, it is desirable to provide an adhesion promoter that enables a wide range of adjustment of adhesion performance and compatibility and overcomes at least one drawback of the prior art.

[0008] Therefore, an object of the present invention was to provide an adhesion promoter that shows good adhesion to a surface and can be modified with the help of being able to adjust its compatibility according to the underlying surface.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] Therefore, an object of the present invention was to provide an adhesion promoter that exhibits good adhesion to the surface and at the same time can be modified with the help of being able to adjust the compatibility according to the underlying surface.

Means for Solving the Problems

[0011] Therefore, in order to achieve the object, a universal adhesion promoter containing a compound based on polybutadiene having at least one repeating unit selected from the group consisting of divalent radicals has been proposed.

Chemical Formula

Chemical Formula

Chemical Formula

Chemical Formula

Chemical Formula

[0012] Adhesion promoters are also known by the terms adhesion additives and / or adhesive resins. [Brief explanation of the drawing]

[0013] [Figure 1] Figure 1 shows the evaluation of a preliminary test using the Andreascutt test. [Modes for carrying out the invention]

[0014] The subject matter of the present invention is described below by example, but the invention is not intended to be limited to these exemplary embodiments. Where ranges, general formulas, or classes of compounds are specified below, these are intended to include not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by deleting individual values ​​(ranges) or compounds. Where any document is referenced in the context of this specification, its entirety is intended to be part of the disclosure of the present invention.

[0015] Where average values ​​are listed below, these values ​​are numerical averages unless otherwise specified. Where measured values, parameters, or material properties determined by measurement are listed below, these are measured values, parameters, or material properties measured at 25°C and preferably at a pressure of 101325 Pa (standard pressure), unless otherwise specified.

[0016] When numerical ranges of the form "X to Y" are listed below, and X and Y represent the limits of the range, this is equivalent to the statement "including at least X to Y" unless otherwise specified. Therefore, the listed ranges include the range limits X and Y unless otherwise specified.

[0017] If a molecule / molecular fragment has one or more stereocenters, and can be distinguished into isomers due to symmetry, or due to other effects, such as rotational restrictions, then all possible isomers are always included in the present invention.

[0018] All formulas describing a compound or radical are constructed from repeating units, such as repeating fragments, blocks, or monomer units, and may have a molar mass distribution. The frequency of repeating units is indicated in the form of an index. The index used in a formula should be considered a statistical mean (numerical mean). Therefore, the range of values ​​of the index used and the reported index should be considered the mean of the possible statistical distributions of the structures that actually exist and / or mixtures thereof. The various fragments or repeating units of a compound described in a formula may be statistically distributed. The statistical distribution may have a block unit structure with any number of blocks and any sequence, or be subject to a randomized distribution. They may also have alternating structures or form a gradient along a chain, where a gradient exists. In particular, they may also give rise to any mixed forms in which groups with different distributions can arbitrarily follow one another. The following formulas contain all permutations of repeating units. Multiple examples of different units of compounds such as polybutadiene (A), epoxy-functionalized polybutadiene (C), hydroxy-functionalized polybutadiene (E), polyether-modified polybutadiene (G), or polyether-modified polybutadiene (K) containing end-capped polyether radicals are described in the context of the present invention, and therefore these may occur in these compounds in an unordered manner, for example, in a statistical distribution, or in an ordered manner. The number of units or numerical values ​​of relative frequencies of such compounds should be considered as the average (numerical mean) of all corresponding compounds. Certain embodiments may, as a result of the embodiment, lead to limitations on the statistical distribution. For all regions not affected by such limitations, the statistical distribution remains unchanged.

[0019] Surprisingly, it has been found that the adhesion promoter according to the present invention advantageously includes non-silicone-based compounds and also offers the possibility of adjusting adhesive performance and fit. Firstly, the versatility of polybutadiene can be utilized. Secondly, fit can be improved by combining specific topologically different polyethers and the density of their functionalities with the polybutadiene backbone.

[0020] The inventors have also been able to establish that the adhesion promoter according to the present invention adheres well to different substrates and has better compatibility than adhesion promoters known from the prior art.

[0021] To achieve both satisfactory adhesive effect and satisfactory fit of the adhesion promoter according to the present invention, it has also been surprisingly established that at least one radical B has at least one repeating unit according to the following:

[0022] [ka]

[0023] The adhesion promoter according to the present invention preferably comprises a compound in which m, n, o, p, and q are each independently from 0 to 100, preferably from 0 to 70, and more preferably from 0 to 50, wherein the sum of m, n, o, p, and q is greater than 1, preferably greater than 5, and more preferably greater than 10.

[0024] The compound for the adhesion promoter according to the present invention preferably has a number-average molar mass M of the polybutadiene portion, with a number-average molar mass of 200 g / mol to 20,000 g / mol, preferably 500 g / mol to 10,000 g / mol, and more preferably 700 g / mol to 5,000 g / mol. n It has.

[0025] The polybutadiene portion of the compound preferably has 0% to 80%, preferably 0% to 30%, more preferably 0% to 10%, and particularly preferably 0% to 5% of the double bonds present as 1,2 vinyl double bonds, and 20% to 100%, preferably 70% to 100%, more preferably 90% to 100%, and particularly preferably 95% to 100% of the double bonds present as 1,4 double bonds. The adhesion promoter according to the present invention preferably contains a compound based on linear polybutadiene. The compound preferably does not contain pendant (com position) polybutadiene. The compound preferably has only the repeating units (U), (V) and / or (W) in the pendant (com position).

[0026] The average molar mass of the B radical is preferably from 100 g / mol to 10,000 g / mol, preferably from 200 g / mol to 7500 g / mol, and particularly preferably from 400 g / mol to 5000 g / mol.

[0027] Radical R 1 , R 2 , R 3 and R 4 can each independently be linear or branched, saturated or unsaturated, aliphatic or aromatic, and substituted or unsubstituted. R = R of formula (4a) 1 or R 2 , or the general notation of R = CH3 in formulas (4b) and (4C)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0028] General notation for equation (4a) [ka] is, formula [ka] Unit or formula [ka] It represents one of the units, but preferably the formula [ka] It represents the unit.

[0029] Furthermore, R 4 In all cases, radicals are monovalent hydrocarbon radicals having 1 to 18 carbon atoms, or acyl radicals (-C(=O)R). 5 , urethane radical-C(=O)NH-R 6 , carbonate radical -C(=O)OR 7 A group independently selected from the group consisting of and hydrogen, and more preferably R 4 In each case, these are an alkyl radical having 1 to 18 carbon atoms, an alkylene radical having 1 to 18 carbon atoms, and an acyl radical -C(=O)R 5 , urethane radical-C(=O)NH-R 6 , carbonate radical -C(=O)OR 7 A group independently selected from the group consisting of and hydrogen, more preferably R 4 It is hydrogen.

[0030] R 5 Each of these is independently an alkyl or alkenyl radical having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably a methyl radical. R 6Each of these is an alkyl or aryl radical having 1 to 18 carbon atoms, preferably 6 to 18 carbon atoms. R 7 Each of these is an alkyl radical having 1 to 18 carbon atoms, preferably 1 or 2 carbon atoms.

[0031] The compound preferably also includes repeating units (Y) and (Z) according to the following: [ka] [ka]

[0032] Here, the value obtained by dividing the sum of all repeating units (U), (V), and (W) in at least one polyether-modified polybutadiene (G) or (K) by the sum of all repeating units (U), (V), (W), (X), (Y), and (Z) is >0% to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and particularly preferably 4% to 20%.

[0033] This means that >0% to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and especially preferably 4% to 20% of the repeating units (U), (V), (W), (X), (Y), and (Z) are polyether-modified.

[0034] Number average molar mass M of the polybutadiene component in polyether-modified polybutadiene (G) or (K) n , weight average molar mass M w , and the degree of polydispersity can change freely. The polybutadiene portion is understood to mean the polyether-modified polybutadiene (G) or (K) component derived from the polybutadiene (A) used in the process.

[0035] Number average molar mass M of the polybutadiene component in polyether-modified polybutadiene (G) or (K) n The concentration is preferably 200 g / mol to 20,000 g / mol, more preferably 500 g / mol to 10,000 g / mol, and more preferably 700 g / mol to 5,000 g / mol.

[0036] Alternatively, the number-average molar mass M of the polybutadiene component of polyether-modified polybutadiene (G) or (K). n The preferred range is 2100 g / mol to 20000 g / mol, particularly preferably 2200 g / mol to 10000 g / mol, and especially preferably 2300 g / mol to 5000 g / mol. Number average molar mass M of the polybutadiene component n Here, the number-average molar mass M of polybutadiene (A) below is... n It is defined as follows.

[0037] The polyether-modified polybutadiene (G) or (K) more preferably has an average of 5 to 360, more preferably 10 to 180, and most preferably 15 to 90 repeating units, where the repeating units are selected from the group consisting of (U), (V), (W), (X), (Y), and (Z).

[0038] Alternatively, the polyether-modified polybutadiene (G) or (K) preferably has an average of 35 to 360, more preferably 40 to 180, and most preferably 45 to 90 repeating units, where the repeating units are selected from the group consisting of (U), (V), (W), (X), (Y), and (Z).

[0039] Polyether-modified polybutadiene (G) or (K) has the following characteristics: 0% to 80%, preferably 0% to 30%, more preferably 0% to 10%, and especially preferably 0% to 5% of the present double bonds are 1,2-vinyl double bonds; and 20% to 100%, preferably 70% to 100%, more preferably 90% to 100%, and especially preferably 95% to 100% of the present double bonds are 1,4 double bonds.

[0040] Therefore, in the context of the present invention, the compound of formula (5) has 0% to 80% 1,2-vinyl double bonds (index a) and 20% to 100% 1,4-double bonds (index b and C combined), based on the total number of repeat units containing double bonds (total of a+b+C), preferably 0% to 30% 1,2-vinyl double bonds and 70% to 100% 1,4-double bonds, more preferably 0% to 10% 1,2-vinyl double bonds and 90% to 100% 1,4-double bonds, and particularly preferably 0% to 5% 1,2-vinyl double bonds and 95% to 100% 1,4-double bonds. The ratio of 1,4-trans double bonds (index b) to 1,4-cis double bonds (index C) can vary freely.

[0041] Particularly preferred is that the compound of formula (5) has a content of >95% of repeating units having exponent d, based on the sum of repeating units d + e + f. The relative ratios of repeating units e and f can vary freely.

[0042] Particularly preferred are the polybutadienes Polyvest® 110 and Polyvest® 130 from Evonik Industries AG / Evonik Operations GmbH, and the polyether-modified polybutadienes (G) or (K) derived from the above-mentioned LitheneultraAL and LitheneActiV 50 from SynthomerPLC.

[0043] The molar mass and polydispersity of B radicals vary freely. However, the average molar mass of B radicals is preferably between 100 g / mol and 20,000 g / mol, more preferably between 200 g / mol and 15,000 g / mol, and more preferably between 400 g / mol and 10,000 g / mol. The average molar mass of B radicals can be calculated from the weight of the monomer used, based on the number of OH groups in the hydroxy-functionalized polybutadiene (E) used. For example, if 40 g of ethylene oxide is used and the amount of hydroxy-functionalized polybutadiene (E) used is 0.05 mol of OH groups, the average molar mass of B radicals is 800 g / mol. Polyether-modified polybutadiene (G) or (K) is liquid, paste, or solid, depending on its composition and molar mass.

[0044] Number average molar mass M of polyether-modified polybutadiene (G) or (K) n Preferably, the concentration is 1000 g / mol to 6000 g / mol, more preferably 1500 g / mol to 5000 g / mol, and particularly preferably 2000 g / mol to 4000 g / mol.

[0045] Their polydispersity varies over a wide range. The polydispersity of at least one polyether-modified polybutadiene (G) or (K) relative to a PPG standard by the GPC method is preferably between 1.5 and 10, more preferably between 2 and 9, and more preferably between 3 and 8. w / M n That is the case.

[0046] As described above, approaches to compounds based on polybutadiene having at least one repeating unit selected from the group consisting of divalent radicals (U), (V), and / or (W) can be derived from the yet unpublished European patent application EP19212066.5 or PCT / EP2020 / 083013.

[0047] An unpublished European patent application EP19212066.5 or PCT / EP2020 / 083013 addresses the preparation of polybutadiene-based compounds suitable as adhesion promoters. The process described therein includes the following steps:

[0048] a) At least one polybutadiene (A) is reacted with at least one epoxidizing reagent (B) to obtain at least one epoxy-functionalized polybutadiene (C).

[0049] b) At least one epoxy-functionalized polybutadiene (C) is reacted with at least one hydroxy-functionalized compound (D) to obtain at least one hydroxy-functionalized polybutadiene (E).

[0050] c) At least one hydroxy-functionalized polybutadiene (E) is reacted with at least one epoxy-functionalized compound (F) to obtain at least one polyether-modified polybutadiene (G).

[0051] Surprisingly, it has been disclosed that polybutadiene, which has a high proportion of 1,4 units and a low content of vinyl 1,2 units after epoxidation with hydrogen peroxide, readily reacts with OH-functional compounds under acid-catalyzed ring-opening to produce pendantly OH-functional polybutadiene (polybutadienol), which can then be alkoxylated with alkylene oxide.

[0052] This process should preferably include at least one of the following optional steps: d) React at least one polyether-modified polybutadiene (G) with at least one end-capping reagent (H) to obtain at least one polyether-modified polybutadiene (K) containing an end-capped polyether radical. e) Brighten the color of at least one polyether-modified polybutadiene (G) or (K).

[0053] This process is preferably, Step a) At least 0% to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and especially preferably 4% to 20% of the double bonds of at least one polybutadiene (A) are epoxidized with the help of performic acid produced in situ from formic acid and H2O2. In step b), one or more short-chain alcohols having 1 to 6 carbon atoms, particularly isobutanol, are added to the epoxy group of at least one epoxy-functionalized polybutadiene (C) under ring-opening conditions, preferably using one or more acidic catalysts, particularly trifluoromethanesulfonic acid. In step c), one or more epoxy-functional compounds (F) selected from alkylene oxides and optionally further epoxy-functional monomers are added to the resulting pendant OH group of at least one hydroxy-functional polybutadiene (E) in the alkoxylation reaction, preferably using a Zn / Co bimetallic cyanide catalyst or a basic catalyst such as an amine, guanidine, amidine, alkali metal hydroxide, or alkali metal alkoxide. In step d), optionally, at least one polyether-modified polybutadiene (G) is reacted with at least one end-capping reagent (H) selected from the group consisting of carboxylic acids, carboxylic acid anhydrides, halogenated hydrocarbons, isocyanates, and carbonates to obtain a polyether-modified polybutadiene (K) containing at least one end-capped polyether radical. In step e), optionally, the color of at least one polyether-modified polybutadiene (G) or (K) is lightened using activated carbon and / or hydrogen peroxide.

[0054] The process disclosed herein makes it possible for the first time to modify linear polybutadiene by simple direct alkoxylation of a pendant OH group having a polyether radical at comb positions. The chain length and monomer sequence of the polyether radical can vary over a wide range. The average number of polyether radicals bonded to polybutadiene can be controlled by the degree of epoxidation and hydroxy-functionalization, opening up structural diversity for hydroxy-functionalized polybutadiene(E).

[0055] The resulting polybutadiene having polyether radicals at the comb positions is preferably essentially free of residual epoxy groups. The process products according to the present invention are preferably essentially free of free polyether components. Preferably, essentially all polyethers are chemically bonded to the polybutadiene via ether bonds. Therefore, the process products according to the present invention are distinctly different from compounds known from the prior art to the present due to their high purity.

[0056] To avoid repetition of the preferred configuration of the preparation process for the yet-to-be-published European patent application EP19212066.5 or PCT / EP2020 / 083013, only the headings of its individual process steps are referenced here. • Preferred configuration of process step a) according to the present invention • Preferred configuration of process step b) according to the present invention • Preferred configuration of process step c) according to the present invention ·DMC catalysis • Basic catalytic action • Products as starters Optional step d) Optional step e) ·reactor Accordingly, the explanations disclosed therein are explicitly incorporated as references.

[0057] As already mentioned above, the suitability of the adhesion promoter according to the present invention can be adjusted by specific topologically different polyether variations and combinations, as well as the density of their functionality on the polybutadiene skeleton. For this reason, it is preferable to describe step c) in detail here.

[0058] In step c) of the method according to the present invention, at least one hydroxy-functionalized polybutadiene (E) is reacted with at least one epoxy-functionalized compound (F) to obtain at least one polyether-modified polybutadiene (G).

[0059] At least one hydroxy-functional polybutadiene (E) from step b) serves as a starter compound for the reaction with at least one epoxy-functional compound (F) in step c). Under ring-opening conditions, preferably in the presence of a suitable catalyst, at least one epoxy-functional compound (F) (hereinafter also simply referred to as "monomer," "epoxy monomer," or "epoxide") is added to the OH group of at least one hydroxy-functional polybutadiene (E) in the polyaddition reaction. This results in the formation of a polybutadiene according to the present invention having a polyether chain at the comb-shaped (pendant) position, i.e., the formation of at least one polyether-modified polybutadiene (G). The polyether-modified polybutadiene (G) is preferably a linear polybutadiene modified with a polyether radical at the comb-shaped (pendant) position. Therefore, it is preferable that the polyether-modified polybutadiene (G) has a linear polybutadiene skeleton and a pendant polyether radical.

[0060] The reaction in step c) is preferably an alkoxylation reaction, i.e., a polyaddition of an alkylene oxide to at least one hydroxy-functionalized polybutadiene (E). However, the reaction in step c) can also be carried out using a glycidyl compound as an alternative or additional to the alkylene oxide.

[0061] Therefore, at least one epoxy-functional compound used in step c) is selected from the group of alkylene oxides, preferably from the group of alkylene oxides having 2 to 18 carbon atoms, more preferably from the group of alkylene oxides having 2 to 8 carbon atoms, particularly preferably from the group consisting of ethylene oxide, propylene oxide, 1-butylene oxide, cis-2-butylene oxide, trans-2-butylene oxide, isobutylene oxide and styrene oxide, and / or at least one epoxy-functional compound used in step c) is selected from the group of glycidyl compounds, preferably from the group of monofunctional glycidyl compounds, more preferably from the group consisting of phenyl glycidyl ether, o-cresyl glycidyl ether, tert-butylphenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12 / C14 fatty alcohol glycidyl ether and C13 / C15 fatty alcohol glycidyl ether.

[0062] In addition to or instead of the alkylene oxides or glycidyl compounds mentioned above, cyclic anhydrides, lactones, dilactines, or cyclic carbonates can also be used as monomers or comonomers with the alkylene oxides or glycidyl compounds already described.

[0063] All cyclic anhydrides known to those skilled in the art can be used in their pure form or in any desired mixture. Saturated, unsaturated, or aromatic cyclic dicarboxylic acid anhydrides are preferably succinic anhydride, octo(en)yl-, dec(en)yl- and dodec(en)ylsuccinic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, trimellitic anhydride, phthalic anhydride, hexahydro-, tetrahydro-, dihydro-, methylhexahydro- and methyltetrahydrophthalic anhydride. The use of succinic anhydride, maleic anhydride, phthalic anhydride and hexahydrophthalic anhydride, particularly maleic anhydride and phthalic anhydride, is especially preferred.

[0064] All lactones known to those skilled in the art, in their pure form or in any desired mixture, can generally be used as lactones. The use of valerolactone, caprolactone, and butyrolactone may be preferred, all of which may be unsubstituted or substituted with organic radicals, preferably methyl groups. The use of ε-caprolactone or δ-valerolactone, particularly ε-caprolactone, is preferred.

[0065] As cyclic carbonates, it is possible to use all cyclic carbonates accessible in pure form or in any desired mixture, generally known to those skilled in the art, via the insertion of CO2 into epoxides. The use of propylene carbonate and ethylene carbonate is preferred.

[0066] Monomers can be added individually in their pure form, alternately and sequentially in any metering sequence, or simultaneously in mixed form. Therefore, the sequence of monomer units in the resulting polyether chain is affected by the block unit distribution, statistical distribution, or gradient distribution of the final product.

[0067] The present invention provides a method by which pendant polyether chains are constructed on polybutadiene, which exemplifies that they can be prepared in a reproducible manner with respect to structure and molar mass. The order of monomer units can be changed by the order of addition within a wide range.

[0068] The molar mass of the pendant polyether radical can vary over a wide range by the process according to the present invention and is specifically and reproducibly controlled with respect to the OH group of at least one initially charged hydroxy-functional polybutadiene (E) from step b) via the molar ratio of the added monomer.

[0069] The polyether-modified polybutadiene (G) prepared according to the present invention is preferably characterized by containing B radicals bonded to the polybutadiene skeleton via ether groups according to formulas (3a), (3b), and (3c). [ka] Formula (3a) [ka] Formula (3b) [ka] Formula (3c)

[0070] As stated in b) above, the A radical in formulas (3a), (3b), and (3c) originates from compound A-OH, i.e., the hydroxy-functional compound (D) used in step b). As also stated above, in step b), it is necessary to distinguish between two cases: A ≠ H or A = H. In the first case, i.e., A ≠ H, the radical A in formulas (3a), (3b), and (3c) is identical to the radical A in formulas (2a), (2b), and (2c). In the second case, i.e., A = H, the radical A in formulas (3a), (3b), and (3c) is independently H or radical B, respectively. For example, when a monofunctional aliphatic alcohol having 1 to 6 carbon atoms is used as the hydroxy-functional compound (D), A is an alkyl radical having 1 to 6 carbon atoms. For example, when a carboxylic acid is used as the hydroxy-functional compound (D), A is an acyl radical. However, when water is used as the hydroxyl-functional compound (D), A in formulas (3a), (3b), and (3c) is the B radical when it reacts with one or more epoxy-functional compounds (F). (If there is no reaction, A remains hydrogen). Thus, each converted pendant hydroxyl group becomes exactly one pendant-OB radical. The radical B then consists of one or more monomers, preferably two or more monomers, of at least one epoxy-functional compound (F) used.

[0071] In the context of the present invention, in principle, all alkoxylation catalysts known to those skilled in the art, such as basic catalysts including alkali metal hydroxides, alkali metal alkoxides, amines, guanidine, amidine, and phosphorus compounds such as triphenylphosphine, and additionally, acid catalysts and Lewis acid catalysts such as SnCl4, SnCl2, SnF2, BF3, and BF3 complexes, and bimetallic cyanide (DMC) catalysts can be used.

[0072] Before supplying the epoxide, i.e., before adding at least one epoxy-functional compound (F) to be used, the reactor, partially filled with the starter and catalyst, is inactivated, for example, with nitrogen. This is achieved, for example, by repeatedly alternating between evacuating and supplying nitrogen. After the final injection of nitrogen, it is advantageous to evacuate the reactor to less than 200 mbar. This means that the addition of the first amount of epoxy monomer is preferably carried out in a vacuum-sealed reactor. To remove the released reaction heat and maintain a pre-selected reaction temperature, the monomer is administered with stirring and optionally cooling. The starter used is at least one hydroxy-functional polybutadiene (E), or, as further described below, a polyether-modified polybutadiene (G) already prepared by the process of the present invention can be used as the starter.

[0073] A second subject of the present invention is the use of adhesion promoters for preparing adhesion promoter compositions. The adhesion promoter compositions preferably have further additives or solvents, which are known to those skilled in the art and can be used.

[0074] A third subject of the present invention is the use of adhesion promoters or adhesion promoter compositions according to the present invention for producing coating materials such as dispersions, mill bases, paints, coatings or printing inks, inkjet printers, pulverized resins, pigment concentrates, colorant preparations, pigment preparations, filler preparations or coating compositions, sealants and adhesive compositions.

[0075] Depending on the overall composition for each application, such as coating materials, sealants, or adhesive compositions, it is preferable to use 0.1 to 50% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight of the adhesion promoter. A fourth subject of the present invention is a process comprising the application of a curable film-forming composition containing an adhesion promoter or adhesion promoter composition according to the present invention.

[0076] The substrate is preferably a composite material such as metal, concrete, wood, and / or glass fiber and / or carbon fiber composite material, a mineral substrate such as steel (variously alloyed and / or post-treated), aluminum, or glass, a dimensionally stable plastic, and / or duromers.

[0077] The adhesion promoter or adhesion promoter composition according to the present invention may preferably be used in a 1K (one-component) coating system or a 2K (two-component) coating system, a melamine baking system, or a room temperature or high temperature system, or a UV system.

[0078] The term "metal substrate" is not exhaustive, but is understood to refer to hot-rolled and cold-rolled steel materials, with or without post-treatment. Untreated steel is degreased before use using a specific cleaner such as GARDOBOND®.

[0079] As the first layer, a chemical solution, for example, Type 26 from GARDOBOND®, can be applied. This is either by spraying (S) or dipping (D). Post-treatment can usually be carried out using an inorganic conversion layer based on phosphate chlorination, alkaline passivation, or chromate. This can be carried out by hot-dip galvanizing or electrolytic galvanizing. For example, an aqueous solution of zinc phosphate can be used. This forms a layer of tertiary zinc phosphate or zinc iron phosphate.

[0080] However, phosphorylation can also be performed. For example, an aqueous solution containing a primary alkali metal phosphate can be used. These sheets can be obtained, for example, from Q-LAB® as type RI.

[0081] Next, a further chemical rinsing solution is used for passivation to ensure a sealed protective layer on the metal. Typically, this is first demineralized water, or various rinsing solutions such as Gardoline® D60, D86, or D6800.

[0082] Aluminum is typically used in cold-rolled aluminum corresponding to grade AlMg 1 G 18. For example, Gardobond® type AA 5005A or Gardobond® grade AlMg 0,4Si 1.2 (automotive specification) type AA6016. Here, the surface is treated with a chromate aqueous solution containing chromic acid. These sheets are available, among other things, from Q-LAB® as type AL. However, galvanized steel can also be further processed using this method.

[0083] The term "glass" is understood to mean inorganic silicate glass, such as borosilicate glass or soda-lime glass, which functions, for example, as beverage bottles. These are usually supplied with labels, or more recently, with direct printing.

[0084] The term "dimensionally stable polymer" is understood, albeit in a non-deterministic sense, to mean the following polymers: acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyether ether ketone (PEEK), polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE), and ethylene propylene diene synthetic rubber mixture (EPDM).

[0085] In a 1K coating system, film formation is achieved by physical drying; therefore, it is preferable that the film-forming polymer does not contain functional groups, or, if drying is performed by a combination of oxidative curing and physical mixing, it is preferable that it does not contain double bonds.

[0086] Purely physically drying film-forming polymers are preferably selected from the group of acrylate polymers, such as Degalan from EVONIK®. When polymers that also cure oxidatively are preferred, they are usually selected from the group of alkyd binders. These are chemically polyesters and are formed by the condensation of alcohols and polyprotic acids to which fatty acids are added to modify their properties. They are distinguished by the oil content level, which controls their drying properties. If the oil content is less than 40%, it is called a short-oil alkyd that dries in the air. If the oil content is between 40% and 60%, it is called a medium-oil alkyd resin and dries in an oven. If the oil content exceeds 60%, a non-drying alkyd is obtained.

[0087] Preferably, in the formulations according to the present invention, for example, a short-oil, air-dryable alkyl resin from WORLEEKyd® is used. Polymerization occurs via double bonds of unsaturated fatty acid esters under the influence of oxygen. Of particular note here is polyunsaturated α-linolenic acid. Desiccants are usually used to accelerate curing. These preferably take the form of octoates, for example, cobalt octoate or calcium octoate. The formulations according to the present invention use a combination of Octa-Soligen® Cobalt 6 and Octa-Soligen® Calcium 10 with OXY Coat from Borchi®, a novel desiccant from BORCHERS®. Cobalt octanoate, trade names Octa-Soligen® Cobalt 10 or Octa-Soligen® Cobalt 12, is also possible. Furthermore, manganese octanoate under the trade name Octa-Soligen® Manganese 10 from BORCHERS®, or zirconium octanoate under the trade name Octa-Soligen® Zirconium 18, are also possible. Manganese octoate (AKDRY Mn Octoate 6%) and zirconium octoate are also available from AMERICANELEMENTS®. Calcium octanoate can also be obtained from PATCHEM® LTD under the trade name Calcium Octoate 10%. In addition, desiccants based on barium, cerium, lithium, or strontium can be used. Today, modern desiccants based on various carboxylic acid metal soaps are available. An example based on 2-ethylhexanoic acid is Octa-Soligen® 203 from BORCHERS®.

[0088] If drying is too rapid, add a so-called de-peeling agent, such as a ketoxime, substituted phenol, or aldoxime. These form a reversible complex with the desiccant. Oximes are available, for example, from BODOMOLLER® CHEMIE under the trade names Dura® MEKO or Duroxim P. Alternatively, butanone oximes are available from FISHERSCIENTIFIC® under the trade name AlfaAesar® 2.

[0089] However, to ensure good processability, it is always necessary to dilute with an appropriate solvent. Xylene is preferably used in the formulation according to the present invention. The use of aliphatic hydrocarbons is also possible.

[0090] In the case of a 2K coating system, the film-forming polymer preferably contains an isocyanate-containing curing agent, an amine-containing curing agent, or a functional group that is reactive with a catalyst.

[0091] The film-forming polymer is preferably selected from the group consisting of hydroxyl-functionalized acrylate polymers, polyester polymers, polyurethane polymers and / or polyether polymers, polyoxypropylene amines, amino-functionalized acrylate polymers or polyester polymers, and polycarbamates that react with an isocyanate-containing curing agent.

[0092] Such polymers typically have reactive hydroxyl groups. It is particularly preferable to use polymers having multiple hydroxyl functional groups. Hydroxyl-functionalized acrylates are available, among others, from Allnex® under the trade names MACRYNAL® or SETALUX®. Examples of hydroxyl-functionalized polyesters are commercially available, among others, under the trade names DESMOPHEN® or SETAL®. Available and commercially available hydroxyl-functionalized polyethers are available, among others, under the trade names TERATHANE® or POLYMEG®. Preferably, the tested 2K coating according to the present invention comprises a curing agent selected from the group of aliphatic or alicyclic isocyanates.

[0093] Examples of isocyanate-containing curing agents include monomer isocyanates, polymer isocyanates, and isocyanate prepolymers. Polyisocyanates are preferred over monomer isocyanates due to their lower toxicity. Examples of polyisocyanates include isocyanurates, uretdiones, and biuret based on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). Examples of commercially available products include DESMODUR® from Covestro or VESTANAT from Evonik Industries, under trade names. Known products include Covestro's DESMODUR® N3200, DESMODUR® N3300, DESMODUR® N3600, DESMODUR® N75, DESMODUR® XP2580, DESMODUR® Z4470, DESMODUR® XP2565, and DESMODUR® VL. Other examples include Evonik Industries' VESTANAT® HAT2500 LV, VESTANAT® HB 2640 LV, or VESTANAT® T1890E. Examples of isocyanate prepolymers include Covestro's DESMODUR® EXP 2863, DESMODUR® XP 2599, or DESMODUR® XP2406. Further isocyanate prepolymers known to those skilled in the art may be used.

[0094] A catalyst may be used for curing. Catalysts selected from organic Sn(IV), Sn(II), Zn, Bi compounds, or tertiary amines can be used.

[0095] It is preferable to use a catalyst selected from the group consisting of organotin catalysts, titanates or zirconates, organometallic compounds of aluminum, iron, calcium, magnesium, zinc, or bismuth, Lewis acids or organic acids / bases, linear or cyclic amidines, guanidines or amines, or mixtures thereof.

[0096] The curing catalyst used is preferably an organotin compound, such as dibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate, or dioctyltin dilaurate, dioctyltin diacetylacetonate, dioctyltin diketanoate, dioctylstannoxane, or dioctyltin oxide, preferably dioctyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, or dioctyltin oxide, particularly preferably dioctyltin dicarboxylate and dioctyltin dilaurate. Furthermore, zinc salts such as zinc octanoate, zinc acetylacetonate, and zinc 2-ethylcaproate, or tetraalkylammonium compounds such as N,N,N-trimethyl-N-2-hydroxypropylammonium hydroxide, N,N,N-trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate, or choline 2-ethylhexanoate may also be used. The use of zinc octoate (zinc 2-ethylhexanoate) and tetraalkylammonium compounds is preferred, with zinc octoate being particularly preferred. Even more preferred is a bismuth catalyst. For example, TIB Kat (TIB Mannheim) or Borchi® catalysts, titanates, e.g., titanium(IV) isopropoxide, iron(III) compounds, e.g., iron(III) acetylacetonate, aluminum triisopropoxide, aluminum trisequbutoxide and other alkoxides, as well as aluminum compounds such as aluminum acetylacetonate, calcium compounds such as calcium disodium ethylenediamine tetraacetate or calcium diacetylacetonate, or amines, e.g., triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, N-ethylmorpholine, and other bismuth catalysts are preferred.Preferred catalysts include organic or inorganic Brønsted acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, or benzoyl chloride, hydrochloric acid, phosphoric acid, and their monoesters and / or diesters, such as butyl phosphate, (iso)propyl phosphate, and dibutyl phosphate. Organic and organosilicon compounds having a guanidine group are also preferred. Of course, it is also possible to use combinations of two or more catalysts. Furthermore, as described in WO2005 / 100482, it is also possible to use photolatent bases as catalysts.

[0097] The curing catalyst is used in an amount preferably 0.01% to 5.0% by weight, more preferably 0.05% to 4.0% by weight, and particularly preferably 0.1% to 3% by weight, based on the total mass of the curable composition.

[0098] The use of solvents may also be useful. These solvents may, for example, help to reduce the viscosity of non-crosslinked binders or facilitate application to surfaces. In principle, the solvents to be considered include all solvents and solvent mixtures. The selection of appropriate solvents is made from the group consisting of alkanes, alkenes, alkynes, benzenes, and aromatic compounds with aliphatic and aromatic substituents, carboxylic acid esters, linear and cyclic ethers, and, under high pressure, hydrocarbons as well, halogenated aliphatic or aromatic hydrocarbons, ketones or aldehydes, lactones (γ-butyrolactone), lactams (e.g., N-methyl-2-pyrrolidone), nitriles, nitro compounds, tertiary carboxamides (dimethylformamide), urea derivatives such as tetramethylurea or dimethylpropylene urea (DMPU), sulfoxides such as dimethyl sulfoxide (DMSO), sulfones such as sulfolanes, and carbonate esters such as dimethyl carbonate and ethylene carbonate. Aprotic solvents such as water, methanol, ethanol, n- and isopropanols and other alcohols, primary and secondary amines, carboxylic acids and their esters, as well as primary and secondary amides such as anhydrides and formamides may also be mentioned. Preferred solvents for coating applications include t-butyl methyl ether, esters such as ethyl acetate or n-butyl acetate, tert-butyl acetate or diethyl carbonate, and ethers such as alcohols such as ethanol and various positional isomers of propanol and butanol. Preferred solvents also include aromatic and / or aliphatic solvents such as benzene, toluene, or naphthacut.

[0099] If necessary, one or more substances selected from the group consisting of cocrosslinking agents, flame retardants, deaeration agents, curing agents, antimicrobial and preservative agents, dyes, colorants and pigments, antifreeze agents, bactericides, spraying aids, wetting agents, fragrances, light stabilizers, free radical scavengers, UV absorbers and stabilizers, in particular stabilizers to counteract thermal and / or chemical stress and / or stress caused by ultraviolet and visible light may be added.

[0100] The UV stabilizer is preferably a known product based on hindered phenols or benzotriazoles. The light stabilizer used may be, for example, one known as a HALS amine. Available stabilizers include products or combinations of products known to those skilled in the art, such as Tinuvin® stabilizer (BASF), for example Tinuvin® 1130, Tinuvin® 292, or Tinuvin® 400, preferably a combination of Tinuvin® 1130 and Tinuvin® 292. The amount used is determined by the required degree of stabilization.

[0101] Suitable pigments for coloring the coating include titanium dioxide and other white pigment-based pigments, inorganic pigments such as iron oxide, organic pigments such as chromium pigments, ultramarine pigments, and azo pigments, phthalocyanine pigments, perylene pigments, quinacridone pigments, and carbon black. Typical anticorrosive pigments such as zinc phosphate are also used to improve corrosion protection.

[0102] The fillers are preferably precipitated or pulverized chalk, common inorganic carbonates, commonly precipitated or pulverized silicates, precipitated or pulverized silica, glass powder, hollow glass beads (called bubbles), metal oxides such as TiO2 and Al2O3, natural or precipitated barium sulfate, finely pulverized quartz, sand, aluminum trihydrate, talc, mica, cristobalite powder, reinforcing fibers such as glass fibers or carbon fibers, long or short fiber wollastonite, cork, carbon black, or graphite. These products allow for the advantageous use of hydrophobic fillers because they reduce water penetration and improve the storage stability of the formulation. The adhesion promoter and adhesion promoter composition according to the present invention may also be used in UV-curable formulations. Here, curing occurs by free radical polymerization.

[0103] The film-forming polymer is preferably selected from the group of acrylates and methacrylates. In most cases, for example, a mixture of polyether acrylate from BASF under the trade name LaromerLR8945® and polyester acrylate from BASF under the trade names LaromerLR8799 or LaromerLR8800® is used. Suitable reactive solvents are hexadiol diacrylate or trimethylolpropane triacrylate. The following embodiments are provided solely to illustrate the invention to those skilled in the art and do not constitute any limitation on the claimed subject matter or the claimed process. I. Adjustment example General method

[0104] Gel permeation chromatography (GPC): Polydispersity (M w / M n ), weight average molar mass (M w ), and number-average molar mass (M n GPC measurements to determine ) were performed under the following measurement conditions: SDV 1000 / 10000A° column combination (length 65 cm), temperature 30°C, THF as mobile phase, flow rate 1 ml / min, sample concentration 10 g / l, RI detector, evaluation against polypropylene glycol standard.

[0105] Measurement of epoxy group content in polybutadiene (epoxy content, epoxidation level) The epoxy group content is, 13 The epoxy content was determined using 13C-NMR spectroscopy. A Bruker Avance 400 NMR spectrometer was used. For this purpose, the sample was dissolved in deuterated chloroform. The epoxy content is defined as the percentage of epoxidized butadiene units in moles, based on the total number of repeating units present in the sample. This corresponds to the number of epoxy groups in the epoxidized polybutadiene divided by the number of double bonds in the polybutadiene used.

[0106] Determination of acid value: The acid value was determined by titration in accordance with DIN ENISO 2114.

[0107] Preparation of an adhesion promoter according to the present invention Steps a) to c) were carried out based on the not yet published European patent application EP19212066.5 or PCT / EP2020 / 083013 1.1. As an example, the first example in each case is described with respect to the weight of the component. The weights used and the parameters of the intermediate and final products are listed in their respective tables.

[0108] Step a) Preparation of epoxidized polybutadiene Epoxidized polybutadiene was prepared using polybutadiene of the brand name Polyvest® 110 (Evonik) with structure x = 1%, y = 24%, and z = 75%.

[0109] A general example of Example A1: In a 5L multi-neck flask, under a nitrogen atmosphere at room temperature, 1500g of Polyvest® 110 and 81.0g of formic acid concentrate in 1500g of chloroform were first added. Subsequently, 300g of a 30% H2O2 aqueous solution (30 wt% H2O2 based on the total mass of the aqueous solution) was slowly added dropwise, and the solution was then heated to 50°C for 5.5 hours. After the reaction was complete, the mixture was cooled to room temperature, the organic phase was removed, and the mixture was washed four times with distilled H2O. Excess chloroform and residual water were removed by distillation. 1440g of product was obtained, which was mixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0110] 13 Evaluation by 13C NMR revealed an epoxidation level of approximately 8.5% of the double bond. w = 4597 g / mol; M n = 1999 g / mol; M w / M n = 2.3 For other examples A2-A4, the weight, reaction conditions, and evaluation are shown in Table 1. For readability, the specifications for examples A1-A4 are left in Table 2.

[0111] [Table 1-1] [Table 1-2]

[0112] Hydroxylated polybutadiene was prepared using epoxidized polybutadiene A1 from step a). The degree of hydroxylation here is determined by dividing the number of OH groups in the hydroxy-functionalized polybutadiene by the number of double bonds in the polybutadiene used in step a). For preparation, 1400 g of epoxidized polybutadiene and 80 μmw of trifluoromethanesulfonic acid (based on the mass of epoxidized polybutadiene) in 1400 g of isobutanol were first packed into a 5 L four-necked flask under a nitrogen atmosphere with stirring. Subsequently, the mixture was heated to 70°C and stirred at this temperature for 6 hours. The reaction mixture became clear during the reaction. After the reaction was complete, the mixture was cooled to room temperature and the solution was neutralized by adding 21.4 g of saturated NaHCO3 solution. The mixture was heated to 115°C and excess water and excess alcohol were removed by distillation under reduced pressure. The alcohol recovered by distillation and dried as needed can be reused in subsequent synthesis. The isobutanol removed by distillation can be dried, for example, by distillation or by adding a desiccant such as molecular sieves. 1455 g of a brownish product was obtained, which was mixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0113] 13 ¹ M w = 6228 g / mol; M n= 2196 g / mol; M w / M n = 2.8 This step was performed similarly in the other examples (see Table 2).

[0114] [Table 2-1] [Table 2-2]

[0115] In a 3-liter autoclave under nitrogen, 334.0 g of hydroxy-functionalized polybutadiene A1 from step b) was first packed, followed by 19.2 g of 30% sodium methoxide solution (30% by weight sodium methoxide in methanol based on the total mass of the solution), and the mixture was stirred at 50°C for 1 hour. Subsequently, the mixture was heated to 115°C while stirring, and the reactor was evacuated to an internal pressure of 30 mbar to remove any excess methanol and other volatile components by distillation. The mixture of 462 g of ethylene (EO) oxide and 351 g of propylene oxide (PO) was continuously weighed and cooled at 115°C for up to 9 hours at an internal reactor pressure of 3.5 bar (absolute). After the reaction at 115°C for 30 minutes, the mixture was degassed. Residual ethylene oxide and propylene oxide and other volatile components were removed by distillation under reduced pressure. The product was cooled to 95°C, neutralized with 30% H3PO4 to an acid value of 0.1 mg KOH / g, and mixed with 1000 ppm Irganox® 1135. Water was removed by distillation under reduced pressure, and the precipitated salt was filtered off. 1076 g of a medium-viscosity, orange-colored, transparent alkoxylated polybutadiene was isolated and stored under nitrogen. M w = 13481 g / mol; M n = 3209 g / mol; M w / M n = 4.2

[0116] Further adhesion promoters according to the present invention and comparative examples were carried out in the same manner as the weight and reaction conditions described in Table 3. Alkoxylation modifications are evident from the "Supply Profile" column.

[0117] [Table 3-1] [Table 3-2]

[0118] General conditions Where values ​​are expressed as % in the context of this invention, they are weight % unless otherwise specified. In the case of compositions, values ​​reported as % are based on the entire composition unless otherwise specified. Where averages are referred to below, they are numerical averages unless otherwise specified. Where measured values ​​are referred to below, these measurements were taken at a pressure of 101-325 Pa, a temperature of 23°C, and an ambient relative humidity of approximately 40%, unless otherwise specified.

[0119] device Hauschild Engineering Speedmixer, Model FAC 150.1 FVZ Drying oven, binder type, equipment type FDL 115 E2 Dispermat, manufactured by Getzmann, equipment type CV2-SIP Crosscut tester, DIN EN ISO 2409, CCP crosscut stencil set HEYCO Model 01664000000 Cutter Knife TESA4651 adhesive tape Lab Balance, Sartorius MSE 6202 S 100 DO BYK Gardner spiral coated bar, 100 μm

[0120] method Adhesion test To optimally test the bonding performance of an adhesion promoter, an initial preliminary test using the Andreas Cut test has proven useful. If the sample is rated as 1 (no minor delamination), a cross-cut test in accordance with DIN ENISO2409 follows. In this way, time and effort are minimized. In some cases, using only the Andreas Cut test value is sufficient. a) Preliminary test using the Andreascat test

[0121] Using a utility knife, cut two notches (scores) 3-4 cm long, at a 90° angle to each other, along a ruler, and penetrate through to the substrate. If using a plastic substrate, take as much care as possible to avoid cutting the substrate. Next, cover the cut areas with TESA adhesive tape 4651, press firmly, and then peel it off. The evaluation is shown in Figure 1. b) Cross-cut testing will be performed in accordance with DIN ENISO2409. The suitability test is determined by visual evaluation of the coating film using a scale (Table 4).

[0122] [Table 4]

[0123] material [Table 5]

[0124] Preparation of coating formulations For application testing, two coating formulations, E1 and E2, corresponding to the components and quantities in Table 6, were first prepared. Coating compound E1:

[0125] The amounts of the components without the hardener (P4) listed in Table 6 (P1 + P5 to P7, P10 + P11, and P13 + P14) were extrapolated to 2 kg. First, P1 was weighed into a 2.5 L sheet metal can. Positions P5 to P7 and P10 to P13 were added sequentially with stirring. The mixture was prepared using a Getzmann disperser mat, instrument type CV2-SIP, on an 8 cm diameter dispersion disc at a speed of 500 rpm, and stirred for a further 20 minutes after the addition of the last position. Care was taken to avoid the observation of smears. Coating compound E2:

[0126] For coating formulation E2, all components except the hardener (P3) (P2 + P6, P8 + P9, and P12 + P14) were extrapolated to 2 kg using the amounts listed in Table 3 and weighed into a 2.5 L volumetric sheet metal can. The mixture was stirred at a speed of 500 rpm using a Getzmann dispermat, instrument type CV2-SIP, with an 8 cm diameter dispersion disc. First, the binder (P2) was added, followed by all other components (P6 + P8 + P9 + P12 + P14) being added while stirring. After the last addition, the mixture was stirred for a further 20 minutes.

[0127] 1) Preparation of coating formulations for application testing The compounds HA1-HA4 of the present invention, comparative examples VGA2 and PV 110 (Polyvest® 110) were each added at 5% by weight based on their respective solid content (E1 = 57.5% by weight; E2 = 56.3% by weight). Coating formulations E1 or E2 without the addition of adhesion promoters served as blank references.

[0128] To incorporate the adhesion promoters HA1-HA4 of the present invention, 20 g of coating formulations E1 and E2 (in a 2K system including curing agent) were weighed into 50 ml PP screw-top jars (Durrmann GmbH&Co KG, 85664 Hohenlinden) for comparative examples VGA2 and PV 110, respectively. The mixture was then mixed for 2 minutes at 2000 rpm using a speed mixer (Hauschild Engineering, type DAC 150 FVZ) (2000 rpm). The prepared coating formulations were then applied to various substrates using a 100 μm spiral coating bar to a dry layer thickness of approximately 40 μm. E1 was applied to glass, Metzler acrylonitrile-butadiene-styrene (ABS), and aluminum A36Q-Panel, respectively. E2 was applied to a steel A36Q panel. The applied substrates were dried and cured overnight at room temperature (23°C), and then dried and cured for 2 days at 60°C.

[0129] [Table 6]

[0130] The results are shown in the following table. [Table 7]

[0131] Coating formulation E1, used as a blank reference, similarly failed to adhere to the glass as expected, as did both comparative examples PV110 and VGA2. Furthermore, the coating film of PV 110 was cloudy and had spots and pinholes.

[0132] The coating formulations having the adhesion promoters HA2 and HA3 according to the present invention exhibited very good compatibility and good adhesion to glass. Since Andreas's cut text only contained "2", a cross-cut test was omitted. Surprisingly, it was found that the adhesive effect could be significantly improved by alkoxylation by adding at least one PO unit.

[0133] [Table 8] Evaluation images for ABS were obtained similar to those for glass. [Table 9]

[0134] The coating formulation containing the adhesion promoter according to the present invention on an aluminum substrate was significantly superior to the comparative coating formulation in at least one property, particularly in terms of compatibility.

[0135] [Table 10]

[0136] Coating formulation E2, which contains the adhesion promoter according to the present invention, showed a clear improvement in adhesion and fit. The examples, quite unexpectedly, demonstrated the universal application of the adhesion promoter according to the present invention.

Claims

1. A universal adhesion promoter comprising a polybutadiene based compound having at least one repeat unit selected from the group consisting of the following divalent radicals: 【Chemical 22】 【Chemistry 23】 【Chemistry 24】 (In the formula, Each A is independently a monovalent organic radical or a hydrogen radical; B is in each case independently selected from the group consisting of radicals of formula (4a): 【Chemistry 25】 Formula (4a) R 1 are independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 16 carbon atoms; R 2 is a radical of formula -CH2-O-R3, R 3 are independently selected from the group consisting of monovalent hydrocarbon radicals having 3 to 18 carbon atoms; R 4 are each independently a monovalent organic radical having 1 to 18 carbon atoms or hydrogen; m, n, o, p and q are each independently 0 to 300, with the proviso that the sum of m, n, o, p and q is greater than 1; Radical B is a group of the formula: 【Chemistry 28】 It has at least one repeating unit conforming to the formula:

2. 2. The universal adhesion promoter of claim 1, wherein m, n, o, p and q are each independently from 0 to 100, with the proviso that the sum of m, n, o, p and q is greater than 1.

3. 2. Adhesion promoter according to claim 1, characterized in that the polybutadiene moiety has a number-average molar mass Mn of from 200 g / mol to 20,000 g / mol.

4. 2. The adhesion promoter of claim 1, wherein from 0 to 80 percent of the double bonds present in the polybutadiene portion are present as 1,2 vinyl double bonds and from 20 to 100 percent are present as 1,4 double bonds.

5. 2. Adhesion promoter according to claim 1, characterized in that the average molar mass of radical B is from 100 g / mol to 10 000 g / mol.

6. 2. The adhesion promoter of claim 1, wherein the compound is prepared on the basis of linear polybutadiene.

7. 2. The adhesion promoter of claim 1, wherein the compound has no pendant polybutadiene at the comb positions.

8. 2. The adhesion promoter of claim 1, characterized in that the compound has pendant repeat units (U), (V) and / or (W) exclusively at the comb positions.

9. 10. Use of the adhesion promoter according to claim 1 for preparing an adhesion promoter composition.

10. 10. Use of the adhesion promoter according to claim 1 or the adhesion promoter composition according to claim 9 for producing dispersions, millbases, paints, coatings or coating materials such as printing inks, ink jets, grinding resins, pigment concentrates, colorants, pigment preparations, filler preparations or coating compositions, sealants and adhesive compositions.

11. 10. A method comprising applying to a substrate a curable film-forming composition comprising the adhesion promoter of claim 1 or the adhesion promoter composition of claim 9.

12. 12. The method of claim 11, wherein the substrate is metal, concrete, wood, glass, plastic, and / or a composite material such as a fiberglass and / or carbon fiber composite.

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