Ladder Copolymer

Abstract

A polymer suitable as an additive having an improved balance of providing desirable and undesirable surface properties is provided. [Solution] The present invention relates to a polymer comprising (a) at least two polymer backbones and (b) at least one polymeric connecting chain having at least two polyether moieties and one polysiloxane moiety, wherein the polysiloxane moiety has a number average molecular weight in the range of 400 to 6000 g / mol, and at least one of the at least two polyether moieties is located between the polymer backbone and the polysiloxane moiety, and the at least two polymer backbones are connected by the at least one polymeric connecting chain.

Description

[Technical field]

[0001] The present invention relates to a polymer having at least two polymer backbone chains and at least one polymeric connector chain, the at least two polymer backbone chains being linked by the at least one polymeric connector chain. The present invention also relates to a method for preparing the polymer, a composition containing the polymer, a coating system formed from the composition, and uses of the polymer. [Background technology]

[0002] WO2019 / 020542A1 relates to a polymer having (a) a polymer backbone and (b) one or more polymeric side chains covalently linked to the polymer backbone, the polymeric side chains having a polyether moiety and a polysiloxane moiety, the polysiloxane moiety having a number average molecular weight in the range of 1050 to 6000, the polyether moiety being located between the polymer backbone and the polysiloxane moiety. The polymers described in this document can be used as additives in coating compositions to modify the surface properties of coatings prepared from the compositions.

[0003] US2019 / 0144588A1 relates to copolymers AB having a moiety derived from a vinyl-terminated polysiloxane A having more than one vinyl group bonded to the polysiloxane and a moiety derived from two or more alkyl esters B of an olefinically unsaturated carboxylic acid, where at least two different alkyl esters B1 and B2 are used, the alkyl group of the first alkyl ester B1 of the olefinically unsaturated carboxylic acid having 1 to 5 carbon atoms and the alkyl group of the second alkyl ester B2 of the olefinically unsaturated carboxylic acid having 6 to 30 carbon atoms, and for the moiety derived from at least one hydroxyalkyl ester B3 of an olefinically unsaturated carboxylic acid, this ester B3 has at least one hydroxyl group in the alkyl group and has 2 to 6 carbon atoms in the alkyl group. This document also relates to their preparation methods and to their use as flow control agents in coating compositions. Summary of the Invention [Problem to be solved by the invention]

[0004] There is a continuing need for improved additives to control the surface properties of compositions. More particularly, there is a delicate balance between desired surface properties, such as slip, leveling, dirt resistance, and self-cleaning properties, on the one hand, and undesirable surface properties, such as poor overcoatability and relatively poor leveling and surface defects such as craters, on the other hand. In many cases, additives that provide one or more desired surface properties also cause undesirable surface properties. The present invention aims to provide polymers suitable as additives with an improved balance between providing desired surface properties and providing undesirable surface properties. Furthermore, polymers suitable as additives should not degrade other properties, such as mechanical properties, weatherability, and corrosion protection. The polymer should be effective in controlling surface properties, preferably when added to the composition in small amounts. [Means for solving the problem]

[0005] The present invention relates to (a) at least two polymer backbones, and (b) at least one polymeric connector chain having at least two polyether moieties and one polysiloxane moiety, the polysiloxane moiety having a number average molecular weight in the range of 400 to 6000 g / mol, and at least one of the at least two polyether moieties being located between the polymer backbone and the polysiloxane moiety; A polymer having the formula: A polymer is provided in which at least two polymer backbone chains are linked by at least one polymeric connector chain. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] The polymer of the present invention is suitable as an additive, with an improved balance between providing desired and undesirable surface properties.In addition, the polymer suitable as an additive does not deteriorate other properties, such as mechanical properties, weather resistance, and corrosion protection.In addition, the polymer is effective in controlling surface properties when added in small amounts into the composition.

[0007] The polymer of the present invention has at least two polymer backbones. The polymer backbones are linear or branched polymers with repeating units. Preferably, the polymer backbones are substantially or entirely linear. In general, the type of polymer forming the polymer backbones is not particularly limited and may be selected from the types of polymers known to those skilled in the art. Examples of suitable polymer types include polyesters, polyurethanes, polycarbonates, and polymers and copolymers of polymerizable ethylenically unsaturated monomers. Considering the wide selection of available ethylenically unsaturated monomers with additional functional groups, polymers and copolymers of such monomers (collectively referred to as (co)polymers) are preferred as the polymer backbones. Examples of suitable ethylenically unsaturated monomers are vinyl esters, vinyl ethers, vinyl aromatic compounds such as styrene, acrylic acid and methacrylic acid and their esters and amides, collectively referred to as (meth)acrylates. In a preferred embodiment, the polymer backbone comprises at least 50% by weight, more preferably at least 75% by weight, of polymerized units of (meth)acrylate.

[0008] The polymer of the present invention generally has a weight average molecular weight in the range of 2000 to 200000 g / mol, preferably 2500 to 150000 g / mol, more preferably 3000 to 100000 g / mol, even more preferably 3500 to 75000 g / mol, even more preferably 4000 to 50000 g / mol, even more preferably 4250 to 25000 g / mol, especially 4500 to 15000 g / mol, most preferably 5000 to 10000 g / mol. The weight average molecular weight of the polymer of the present invention can be determined by GPC using polystyrene standards and tetrahydrofuran as an eluent.

[0009] In the polymer of the present invention, at least two polymer backbone chains are linked by at least one polymeric connecting chain. Generally, the polymeric connecting chain covalently connects the polymer backbone chains. The resulting structure may also be referred to as a ladder polymer. Typically, two or more polymeric connecting chains are covalently connected to the polymer backbone. The polymeric connecting chain has at least two polyether moieties and one polysiloxane moiety. At least one of the at least two polyether moieties is located between the polymer backbone and the polysiloxane moiety. In one aspect, the polymeric connecting chain consists essentially of two polyether moieties and one polysiloxane moiety. In another embodiment, the two polyether moieties are located between the polymer backbone and the polysiloxane moiety. In other embodiments, the polymeric connecting chain may have additional moieties. Examples of additional moieties include polyester moieties. In one embodiment, each polymeric connecting chain has the same type of moiety. In another embodiment, there may be polymeric connecting chains with different types of moieties.

[0010] The polysiloxane portion of the polymeric connecting chain has a number average molecular weight in the range of 400 to 6000 g / mol, preferably 900 to 4000 g / mol, and more preferably 1000 to 3000 g / mol. This number average molecular weight range of the polysiloxane portion is believed to provide an improved balance between desirable and undesirable surface properties.

[0011] The polysiloxane portion generally has the formula -[OSiR 1 R 2 The number of repeating units is generally within the range of 4 to 80. 1 and R 2 The groups R are each independently an alkyl group having 1 to 8 carbon atoms, an aryl group selected from phenyl and alkylphenyl, where alkylphenyl has 1 to 9 carbon atoms in the alkyl group. 1 and R 2 represents a methyl group.

[0012] The polyether portion generally has a number average molecular weight in the range of 88 to 3000 g / mol, in a preferred embodiment 132 to 2000 g / mol, more preferably 132 to 1000 g / mol.

[0013] The polyether moiety generally comprises polymerized units of alkylene oxide. The alkylene oxide is preferably selected from ethylene oxide, propylene oxide, and combinations thereof. Particularly preferably, the polyether moiety comprises or consists of polymerized units of ethylene oxide. When the polyether moiety comprises polymerized units of more than one alkylene oxide, such units may be arranged statistically (randomly), in a gradient, or in blocks. The number of polymerized alkylene oxides in the polyether moiety is generally in the range of 1 to 70, for example, 3 to 45, or 5 to 22.

[0014] The number average molecular weight of the polysiloxane and polyether moieties can be determined using GPC.

[0015] In a preferred embodiment, at least one of the polymer backbones of the polymers of the invention has at least one lateral polymer chain comprising at least two polyether moieties and one polysiloxane moiety, the polysiloxane moiety having a number average molecular weight in the range of 400-6000 g / mol, and at least one of the at least two polyether moieties being located between the polymer backbone and the polysiloxane moiety.

[0016] Generally, the polymers of the invention contain 2 to 4 lateral polymer chains as described above.

[0017] In some embodiments, the polymer of the present invention has a functional group, in particular a functional group that can participate in the curing reaction of the composition to which the polymer of the present invention is added for improving surface properties. The type of functional group is not particularly limited and may be selected to match the functional groups that may be present in the composition to which the polymer is added. In a preferred embodiment, the polymer has a functional group that includes at least one of a hydroxyl group, a carboxylic acid group, an amino group, an etherified amino group, an amide group, an epoxide group, and an alkoxysilyl group.

[0018] Preferably, the polymers of the present invention have at least one hydroxyl group per molecule and have a hydroxyl number in the range of 1 to 250 mg KOH / g, preferably 5 to 200 mg KOH / g, more preferably 10 to 100 mg KOH / g.

[0019] The polysiloxane content of the polymer of the present invention is generally in the range of 0.5 to 5.0% by weight, calculated based on the weight of the polymer. In a preferred embodiment, the polysiloxane content is in the range of 1.0 to 4.5% by weight, more preferably in the range of 1.5 to 4.0% by weight.

[0020] The acid value of the polymer is generally within the range of 0.0 to 30.0 mg KOH / g.

[0021] Further subject matter of the invention are: (a) a polymer according to the present invention in an amount of 0.01 to 15.00% by weight, based on the total non-volatile content of the composition; (b) a binder different from the polymer (a) A composition comprising:

[0022] The above compositions preferably contain the polymer of the present invention in an amount of 0.01 to 10 wt. %, preferably 0.20 to 8.00 wt. %, more preferably 0.30 to 7.00 wt. %, or 0.30 to 6.00 wt. % or 0.30 to 5.00 wt. %, in particular 0.50 to 5.00 wt. %, based on the total weight of the non-volatile contents of the composition.

[0023] The polymers of the present invention may be contained in the composition as a 100% substance, as a solution, as a dispersion, or as an emulsion.

[0024] The properties of the compositions, in particular the properties of coating compositions, molding compositions and cosmetic formulations, are not hindered by the amount of the polymers of the invention described herein.The presence or use of these polymers does not have a detrimental effect, for example in terms of the corrosion protection, gloss retention, weather resistance and / or mechanical strength of the coatings obtained from these compositions.

[0025] The polymers of the present invention are highly suitable for controlling the surface properties in compositions, such as coating compositions, molding compositions, prepolymer compositions, cosmetic formulations, etc. The present invention therefore also relates to the use of the polymers of the present invention as additives in compositions for controlling one or more properties of the composition selected from leveling, surface slip, crater (denting), telegraph, overcoatability, cratering, open time, dirt adhesion, self-cleaning, air ventilation sensitivity, haze properties, and static properties.

[0026] Cipping is a coating defect that can be defined as droplets or lines of wet film collecting together, leaving some of the surface with no coating or incomplete coverage. The surface to be coated can be the surface of a substrate or the surface of an already applied coating layer. Cipping can occur with organic solvent-based coatings and also with water-based coatings.

[0027] The present invention therefore also relates to the use of the polymer according to the present invention as an additive in a composition for controlling one or more properties of the composition selected from leveling, surface slip, crater (denting), telegraph, overcoatability, cissing, open time, dirt adhesion, self-cleaning, air venting sensitivity, haze properties, and static properties. This use can also be described as a method for controlling one or more of the above properties of a composition, which method comprises adding the polymer according to the present invention to the composition. In a preferred embodiment, the polymer according to the present invention is added in an amount of 0.01 to 15.00% by weight, based on the total non-volatile content of the composition.

[0028] In a still further aspect, the present invention relates to a method for preparing the polymer of the present invention.

[0029] In a preferred embodiment, the method of preparing the polymers of the present invention comprises polymerizing a monomer mixture comprising: (a) a polyether-modified polysiloxane having at least two polyether moieties and at least two polymerizable ethylenically unsaturated groups bonded to at least two of the at least two polyether moieties, and one polysiloxane moiety, wherein the polysiloxane moiety has a number average molecular weight in the range of 400 to 6000 g / mol, and the polysiloxane moiety is located between the at least two polyether moieties; (b) at least one other additional monomer having one polymerizable ethylenically unsaturated group.

[0030] A polyether-modified polysiloxane having at least two polyether moieties and at least two polymerizable ethylenically unsaturated groups attached to at least two of the at least two polyether moieties is suitably prepared by: (i) provide: (a) a monomer having one polymerizable ethylenically unsaturated group and one further functional group different from the polymerizable ethylenically unsaturated group, and (b) a molecule having two groups reactive toward the one additional functional group, at least two polyether moieties, and a polysiloxane moiety, the polysiloxane moiety having a number average molecular weight in the range of 400 to 6000, the polyether moiety being located between the group reactive toward the one additional functional group and the polysiloxane moiety; (ii) forming two covalent bonds between said monomer (a) and said molecule (b) by reacting two further functional groups with groups reactive towards said one further functional group.

[0031] In a further embodiment, a polyether-modified polysiloxane having at least two polyether moieties and at least two polymerizable ethylenically unsaturated groups attached to at least two of the at least two polyether moieties is prepared by: (i) provide: (a) a monomer having one polymerizable ethylenically unsaturated group, a polyether moiety, and one further ethylenically unsaturated functional group different from the polymerizable ethylenically unsaturated group, the polyether moiety being located between the polymerizable ethylenically unsaturated group and the further ethylenically unsaturated functional group; (b) a molecule having a number average molecular weight in the range of 400 to 6000 and a polysiloxane moiety having at least two Si—H groups; (ii) forming a covalent bond between said monomer (a) and said molecule (b) by a hydrosilylation reaction of a Si-H group on said further ethylenically unsaturated functionality.

[0032] For a more detailed description of such methods, reference is made to International Patent Application WO2017 / 036612, in particular pages 13 to 48 of this publication.

[0033] The present invention further relates to a composition comprising: (a) a polymer of the present invention in an amount of 0.01 to 15.00 weight percent, based on the total nonvolatile content of the composition; (b) a binder different from the polymer (a).

[0034] The composition preferably contains the polymer according to the present invention in an amount of 0.01 to 10.00% by weight, preferably 0.20 to 8.00% by weight, more preferably 0.30 to 7.00% by weight, or 0.30 to 6.00% by weight or 0.30 to 5.00% by weight, in particular 0.50 to 5.00% by weight, each based on the total weight of the non-volatile contents of the composition.

[0035] The polymers of the present invention may be contained in the composition as the 100% material, as a solution, as a dispersion, or as an emulsion.

[0036] The properties of the compositions, in particular the properties of coating compositions, molding compositions and cosmetic formulations, are not hindered by the amount of the polymers of the present invention present therein. The presence or use of these polymers does not have a detrimental effect, for example, on the corrosion resistance, gloss retention, weather resistance and / or mechanical strength of the coatings obtained from these compositions.

[0037] In typical embodiments, the composition is liquid at ambient temperature, for example at a temperature of 20° C. In some embodiments, the polymer according to the invention and / or the binder present in the composition are liquid. In such cases, the composition may be liquid at ambient temperature without the need for a liquid volatile diluent. In other embodiments, it may be necessary or desirable to make the composition liquid or to achieve a desired viscosity by including a volatile diluent. The volatile diluent may be water or an organic solvent, or a mixture thereof. Thus, the composition may be an aqueous composition or a non-aqueous composition.

[0038] The composition of the present invention contains at least one binder. All conventional binders known to those skilled in the art are suitable as the binder component of the composition of the present invention. The binder used according to the present invention preferably has a crosslinkable functional group. Any conventional crosslinkable functional group known to those skilled in the art is considered here. More particularly, the crosslinkable functional group is selected from the group consisting of hydroxyl groups, amino groups, carboxylic acid groups, and unsaturated carbon double bonds, isocyanates, polyisocyanates, and epoxides, such as ethylene oxide. The binder may be exothermically or endothermally crosslinkable or curable. The binder is preferably crosslinkable or curable within a temperature range of -20°C to 250°C. The binder is preferably selected from the group consisting of epoxide resins, polyesters, which may be unsaturated, vinyl ester-based resins, poly(meth)acrylates, polyurethanes, polyureas, polyamides, polystyrenes, polyethers, polycarbonates, polyisocyanates, and melamine formaldehyde resins. These polymers may be homopolymers or copolymers. These resins and their preparation are known to those skilled in the art.

[0039] The compositions of the present invention may be provided as a one-component system or as a two-component system.

[0040] The composition of the present invention preferably comprises a binder in an amount of 3 to 90% by weight, preferably in an amount of 5 to 80% by weight, more preferably in an amount of 10 to 75% by weight, based on the total weight of the composition.

[0041] Depending on the desired application, the composition of the present invention may have as components one or more commonly used additives. These additives are preferably selected from the group consisting of emulsifiers, flow control aids, solubilizers, defoamers, stabilizers (preferably heat stabilizers, process stabilizers, and UV and / or light stabilizers), catalysts, waxes, softeners, flame retardants, reactive diluents, adhesion promoters, organic and / or inorganic nanoparticles with a particle size of less than 100 nm, process aids, plasticizers, fillers, glass fibers, reinforcing materials, additional wetting agents and dispersants, light stabilizers, ageing agents, and mixtures of the above additives. The content of the above additives in the composition of the present invention may vary over a very wide range depending on the intended use. The content, calculated based on the total weight of the composition of the present invention, is preferably 0.01 to 10.00% by weight, more preferably 0.01 to 8.00% by weight, very preferably 0.01 to 6.00% by weight, particularly preferably 0.01 to 4.00% by weight, especially 0.01 to 2.00% by weight. The composition of the present invention may be used in a pigmented or unpigmented form and may contain fillers, such as calcium carbonate, aluminum hydroxide, and reinforcing fibers, such as glass fibers, carbon fibers, and aramid fibers.

[0042] The coating compositions of the present invention are preferably coating compositions for producing antistatic coatings, anti-fog coatings, self-cleaning facade coatings, automotive coatings, dirt equipment coatings, marine coatings (fouling resistant coatings) and primer coatings.Due to the outstanding compatibility of the copolymers, they are also outstandingly suitable for producing transparent coatings.

[0043] The compositions of the present invention can be applied to a number of substrates, including wood, paper, glass, ceramic, gypsum, concrete, and metal. In a multiple coating process, the coating may be applied to a primer, a primer top, or an undercoat. Curing of the composition depends on the particular type of crosslinking and may occur within a wide range of temperatures, for example, from -10°C to 250°C. In a preferred embodiment, the substrate is an automobile or part thereof. Examples of automobiles are cars, buses, trucks, trains, aircraft, and motor-driven agricultural and construction equipment.

[0044] The inventive molding compound, which is preferably polymeric, preferably comprises at least one polymer selected from the group consisting of lacquer resins, alkyd resins, polyester resins, epoxy resins, polyurethane resins, unsaturated polyester resins, vinyl ester resins, polyethylene, polypropylene, polyamide, polyethylene terephthalate, PVC, polystyrene, polyacrylonitrile, polybutadiene, polyvinyl chloride, or mixtures of these polymers, or any copolymers thereof.

[0045] When the composition containing the polymer of the present invention is a coating composition, the coating composition is very suitable for preparing a multi-layer coating system (multi-layer coating system) on a substrate. The multi-layer coating system comprises at least one undercoat layer and at least one topcoat layer, at least one layer being based on the composition of the present invention. In a preferred embodiment, the undercoat layer and the topcoat layer are based on the composition of the present invention. Preferably, the undercoat layer and the topcoat layer have a common layer boundary. The undercoat layer and the topcoat layer may be prepared from different coating compositions, for example, a pigment-based coating composition for the undercoat layer and a pigment-free clearcoat composition for the topcoat layer. Alternatively, the undercoat layer and the topcoat layer may be prepared from the same coating composition. In a preferred embodiment, the substrate is an automobile or its parts.

[0046] A further subject of the present invention is a method for producing a multi-layer coating system on a substrate, comprising the steps of: (i) applying a coating composition (a) to a substrate to form a coating layer (a); and (ii) applying a coating composition (b) to form a coating layer (b) on coating layer (a); wherein at least one of coating composition (a) or coating composition (b) comprises the polymer of the present invention in an amount of 0.01 to 15.00 wt. %, based on the total non-volatile content of the coating composition. EXAMPLES

[0047] raw materials Isobutanol (iBuOH) was used as the solvent for all polymerizations.

[0048] [Table 1]

[0049] The number-average and weight-average molecular weights and molecular weight distributions were determined at 40°C according to DIN 55672-1:2007-08 using a high-pressure liquid chromatography pump (WATERS 600 HPLC pump) and a refractive index detector (Waters 410). A combination of three Styragel columns from WATERS with a size of 300 mm x 7.8 mm ID / column, a particle size of 5 μm, and pore sizes HR4, HR2 and HR1 was used as the separation column. The eluent used for the copolymers was tetrahydrofuran filtered through a 0.2 μm membrane filter at an elution rate of 1 ml / min. Routine calibration was performed using polystyrene standards. The molecular weights reported and referred to in this description always have the unit g / mol.

[0050] General Procedure for Preparation of Comparative Examples C1 and C2 The required amounts of solvent and monomer are specified in Table 1. Reflux condenser, temperature sensor, N 2 In a four-necked round glass flask connected to a gas inlet and a dropping funnel, isobutanol was added at constant N 2 The mixture was heated to reflux (about 107° C.) under a gas flow. Monomer and azobisisobutyronitrile (4 parts) as initiator were homogenized and metered into the reaction mixture at a uniform rate over a period of 3 hours. After completion of the addition, the reaction temperature was maintained at reflux conditions for 0.5 hours. Then, two portions of azobisisobutyronitrile (0.1 parts) were added at 1 hour intervals. After stirring the reaction mixture under reflux conditions for 1 hour, the reaction mixture was cooled to ambient conditions. The product was characterized by gel permeation chromatography and the Mw was determined (Table 1).

[0051] Procedure for preparation of Comparative Example C3 Reflux condenser, temperature sensor, N 2 In a four-neck round glass flask connected to a gas inlet and a dropping funnel, 34.7 parts of isobutanol were added to a constant N 2 The mixture was heated to reflux (about 107° C.) under a gas flow. 24 parts of 2-ethylhexyl acrylate, 23 parts of butyl acrylate, 10.2 parts of hydroxyethyl methacrylate, and azobisisobutyronitrile (4 parts) as radical initiator were homogenized and metered into the reaction mixture at a uniform rate over a period of 3 hours. After completion of the addition, the reaction temperature was maintained at reflux conditions for 0.5 hours. Then, two portions of azobisisobutyronitrile (0.1 parts) were added at intervals of 1 hour. After stirring the reaction mixture under reflux conditions for 1 hour, the reaction mixture was cooled to ambient conditions. 4 parts of silicone component 2 were added and the mixture was homogenized for 5 minutes. The product was characterized by gel permeation chromatography (Mw=5595 g / mol).

[0052] General Procedure for the Preparation of Examples E1-E3 The required amounts of solvent and monomer are specified in Table 1. Reflux condenser, temperature sensor, N 2 In a four-necked round glass flask connected to a gas inlet and a dropping funnel, isobutanol was added at constant N2 The mixture was heated to reflux (about 107° C.) under a gas flow. Monomer, chain transfer agent (optional), and azobisisobutyronitrile (4 parts) as initiator were homogenized and metered into the reaction mixture at a uniform rate over a period of 3 hours. After completion of the addition, the reaction temperature was maintained at reflux conditions for 0.5 hours. Then, two portions of azobisisobutyronitrile (0.1 parts) were added at 1 hour intervals. After stirring the reaction mixture under reflux conditions for 1 hour, the reaction mixture was cooled to ambient conditions. The product was characterized by gel permeation chromatography and the Mw was determined (Table 1).

[0053] [Table 2]

[0054] The preparation of the solvent-based clearcoat is divided into several steps for better clarity. This process is (a) Preparation of Liquid Formulations (b) Application, curing, and evaluation It is.

[0055] Preparation of Solvent-Based Clearcoat Liquid Formulations

[0056] [Table 3]

[0057] The materials shown in Table 2 were mixed and homogenized to form the binder component and the crosslinking component.

[0058] The binder components were then separated into portions and one of the inventive polymers or one of the comparative polymers was added and mixed in. The amount of polymer added was 0.3% by weight of added polymer, calculated based on the binder components.

[0059] The clearcoat composition was prepared by mixing the binder and crosslinking components in a 2:1 weight ratio.

[0060] Application, Curing and Evaluation The clearcoat composition was applied to a steel panel in the form of a 50 μm thick wet film using a spiral film applicator. The applied clearcoat was dried and cured at room temperature for 24 hours.

[0061] The coefficient of friction (COF) was determined with an Altek instrument using a 500 g weight and self-adhesive felt. The instrument reading was multiplied by a factor of 0.02.

[0062] Overcoatability was tested by applying a second clearcoat layer on top of the cured clearcoat. This second clearcoat layer did not contain the inventive or comparative polymer. The flow and leveling of this second clearcoat layer was judged on a scale of 1 (very good) to 5 (poor). The leveling of the first layer was determined using a Wavescan instrument ex BYK-Gardner. Longwave (LW) and shortwave (SW) values ​​were recorded.

[0063] Crater formation on each layer was visually judged on a scale of 1 (no cratering) to 5 (severe cratering).

[0064] The haze of each coating layer was visually judged on a scale of 1 (no haze) to 5 (severe haze).

[0065] Cross-cut adhesion tests were performed according to DIN EN ISO 2404. Results are reported on a rating scale of 1 (no delamination) to 5 (severe delamination).

[0066] The results are summarized in Table 3.

[0067] [Table 4]

[0068] From Table 3, it can be concluded that the comparative polymer C1 without silicone has no beneficial effect. The comparative polymer C2 according to US2019 / 0144588A has a beneficial effect on leveling. However, the amount of crater formation is insufficient. Also, the leveling and cross-cut adhesion of the second layer are insufficient. The comparative polymer C3 causes poor cross-cut adhesion of the second layer.

[0069] Polymers E1 and E2 according to the invention show a very good overall balance of improved properties, in particular good levelling, no cratering and good adhesion of the second layer.

[0070] A further series of tests was carried out with the clearcoat applied by airless spray to primed steel panels. The wet film thickness was 80 μm. The levelling was determined with a Wavescan instrument. Short and long wave readings were recorded. The results are summarized in Table 4.

[0071] [Table 5]

[0072] Comparative polymer C1, which had no silicone, provided a surface with such poor leveling that it could not be measured using the Wavescan instrument. Comparative polymer C2 had a good effect on leveling, but was poor in shortwave measurements.

[0073] The polymers E1, E2 and E3 according to the invention provide an overall improved levelling property. The present disclosure includes the following aspects: <Aspect 1> (a) at least two polymer backbones, and (b) at least one polymeric connector chain having at least two polyether moieties and one polysiloxane moiety, the polysiloxane moiety having a number average molecular weight in the range of 400 to 6000 g / mol, and at least one of the at least two polyether moieties being located between the polymer backbone and the polysiloxane moiety; A polymer having the formula: the at least two polymer backbone chains are connected by the at least one polymeric connector chain; The polymer has a weight average molecular weight in the range of 2000 to 200000 g / mol as determined by GPC using polystyrene standards and tetrahydrofuran as an eluent. polymer. <Aspect 2> at least one of the polymer backbones has at least one lateral polymer chain having at least two polyether moieties and one polysiloxane moiety, the polysiloxane moiety having a number average molecular weight in the range of 400-6000 g / mol, and at least one of the at least two polyether moieties is located between the polymer backbone and the polysiloxane moiety; 2. The polymer of embodiment 1. <Aspect 3> 3. The polymer of embodiment 1 or 2, wherein the polysiloxane portion has a number average molecular weight in the range of 900 to 4000 g / mol. <Aspect 4> The polymer of any one of embodiments 1 to 3, wherein the polymer backbone is a (co)polymer of a polymerizable ethylenically unsaturated monomer. <Aspect 5> The polymer of any one of aspects 1 to 4, wherein the polyether moieties, independently of each other, have a number average molecular weight in the range of 88 to 3000 g / mol. <Aspect 6> 6. The polymer of any one of the preceding embodiments, wherein the polyether portion has polymerized units of an alkylene oxide selected from ethylene oxide, propylene oxide, and combinations thereof. <Aspect 7> 7. The polymer of any one of the preceding claims, wherein the polymer further comprises functional groups comprising at least one of a hydroxyl group, a carboxylic acid group, an amino group, an etherified amino group, an amide group, an epoxide group, and an alkoxysilyl group. <Aspect 8> A method for preparing the polymer according to embodiment 4, comprising polymerizing a monomer mixture comprising: (a) a polyether-modified polysiloxane having at least two polyether moieties and at least two polymerizable ethylenically unsaturated groups attached to at least two of the at least two polyether moieties, and one polysiloxane moiety, wherein the polysiloxane moiety has a number average molecular weight in the range of 400 to 6000 g / mol, and the polysiloxane moiety is disposed between the at least two polyether moieties, a polyether-modified polysiloxane, and (b) at least one further monomer having one polymerizable ethylenically unsaturated group. <Embodiment 9> The monomer mixture further comprises a polyether-modified polysiloxane, which has at least two polyether moieties and one polymerizable ethylenically unsaturated group attached to one of the at least two polyether moieties, and one polysiloxane moiety, wherein the polysiloxane moiety has a number average molecular weight in the range of 400 to 6000 g / mol, and the polysiloxane moiety is located between the at least two polyether moieties, The method according to embodiment 8. <Embodiment 10> (a) the polymer according to any one of embodiments 1 to 7 in an amount of 0.01 to 15.00% by weight based on the total non-volatile content of the composition, and (b) a binder different from the polymer (a) A composition comprising. <Embodiment 11> The composition according to embodiment 10, wherein the composition is liquid at a temperature of 20°C and contains a volatile diluent. <Embodiment 12> A multi-layer coating system on a substrate having at least one undercoat layer and at least one topcoat layer, wherein at least one layer is formed from the composition according to embodiment 10 or 11. <Embodiment 13> The multi-layer coating system according to embodiment 12, wherein the substrate is an automobile or a part thereof. <Embodiment 14> A method for forming a multi-layer coating system on a substrate, comprising: (i) applying a coating composition (a) to the substrate to form a coating layer (a), and (ii) applying a coating composition (b) to form a coating layer (b) on the coating layer (a). comprising At least one of the coating compositions (a) or (b) contains the polymer according to any one of the embodiments 1 to 7 in an amount of 0.01 to 15.00 wt. %, based on the total non-volatile content of the coating composition. method. <Aspect 15> 8. Use of the polymer according to any one of the preceding aspects as an additive in a composition to control one or more properties of the composition selected from leveling, surface slip, crater, telegraph, overcoating, cissing, open time, dirt adhesion, self-cleaning, air ventilation sensitivity, haze, and static properties.

Claims

1. (a) at least two polymer backbone chains, and (b) at least one polymeric connecting chain having at least two polyether moieties and one polysiloxane moiety, wherein the polysiloxane moiety has a number average molecular weight in the range of 400 to 6000 g / mol, and at least one of the at least two polyether moieties is located between the polymer backbone chain and the polysiloxane moiety, at least one polymeric connecting chain, A polymer having The at least two polymer backbone chains are connected by the at least one polymeric connecting chain, The polymer has a weight average molecular weight in the range of 4500 to 15000 g / mol as determined by GPC using a polystyrene standard and tetrahydrofuran as an eluent, The polyether moiety has polymerized units of alkylene oxide, and The number of polymerized units of alkylene oxide in each of the polyether moieties is 5 to 22, The polymer backbone chain is a copolymer containing at least 50% by weight of polymerized units of (meth)acrylate.

2. The polymer according to claim 1, wherein the polymer backbone chain is a copolymer containing at least 75% by weight of polymerized units of (meth)acrylate.

3. At least one of the polymer backbone chains has at least one lateral polymer chain having at least two polyether moieties and one polysiloxane moiety, the polysiloxane moiety has a number average molecular weight in the range of 400 to 6000 g / mol, and at least one of the at least two polyether moieties is located between the polymer backbone chain and the polysiloxane moiety, The polymer according to claim 1 or 2.

4. The polymer according to any one of claims 1 to 3, wherein the polysiloxane moiety has a number average molecular weight in the range of 900 to 4000 g / mol.

5. The polymer according to any one of claims 1 to 4, wherein the polyether moieties independently have a number average molecular weight in the range of 88 to 3000 g / mol.

6. The polymer according to any one of claims 1 to 5, wherein the alkylene oxide is selected from ethylene oxide, propylene oxide, and combinations thereof.

7. 7. The polymer of claim 1, further comprising functional groups comprising at least one of a hydroxyl group, a carboxylic acid group, an amino group, an etherified amino group, an amide group, an epoxide group, and an alkoxysilyl group.

8. A method for preparing a polymer according to any one of claims 1 to 7, comprising polymerising a monomer mixture comprising: (a) a polyether-modified polysiloxane having at least two polyether moieties and at least two polymerizable ethylenically unsaturated groups attached to at least two of the at least two polyether moieties, and a polysiloxane moiety, the polysiloxane moiety having a number average molecular weight in the range of 400 to 6000 g / mol, the polysiloxane moiety being disposed between the at least two polyether moieties; and (b) at least one other additional monomer having one polymerizable ethylenically unsaturated group.

9. the monomer mixture further comprises a polyether-modified polysiloxane having at least two polyether moieties and a polymerizable ethylenically unsaturated group bonded to one of the at least two polyether moieties, and a polysiloxane moiety; the polysiloxane moiety has a number average molecular weight in the range of 400 to 6000 g / mol, and the polysiloxane moiety is located between the at least two polyether moieties; The method according to claim 8.

10. A composition comprising: (c) a polymer according to any one of claims 1 to 7 in an amount of 0.01 to 15.00 wt. %, based on the total non-volatile content of the composition; and (d) a binder different from the polymer (c) A composition comprising:

11. The composition of claim 10, wherein the composition is liquid at a temperature of 20° C. and contains a volatile diluent.

12. 12. A multi-layer coating system on a substrate having at least one undercoat layer and at least one topcoat layer, wherein at least one layer is formed from the composition of claim 10 or 11.

13. The multi-layer coating system of claim 12, wherein the substrate is an automobile or part thereof.

14. 1. A method for forming a multi-layer coating system on a substrate, comprising: (i) applying a coating composition (e1) to a substrate to form a coating layer (e2); and (ii) applying a coating composition (f1) to form a coating layer (f2) on the coating layer (e2); Including, At least one of the coating compositions (e1) or (f1) contains the polymer according to any one of claims 1 to 7 in an amount of 0.01 to 15.00 wt.-%, based on the total non-volatile content of the coating composition. method.

15. 8. Use of the polymer according to any one of claims 1 to 7 as an additive in a composition to control one or more properties of said composition selected from levelling, surface slip, crater, telegraph, overcoating, cissing, open time, dirt adhesion, self-cleaning, air ventilation sensitivity, haze and static properties.

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