Non-aqueous bridging components

Abstract

Provided are a particulate polyurea compound a2) for reducing the gloss of coatings, a resin composition containing the particulate polyurea compound, and a crosslinkable composition, wherein the volume percentage of particles of the particulate polyurea compound having a diameter of less than 10 μm is 40% or less, and the volume percentage of polyurea products having a diameter of more than 20 μm is 11% or more.

Description

[Technical Field]

[0001] The present invention relates to particulate polyurea compounds capable of providing coatings with reduced gloss, and resin compositions comprising such polyurea compounds. The present invention also relates to crosslinkable compositions comprising such resin compositions, methods for coating substrates with the crosslinkable compositions to obtain coated substrates with reduced gloss, and substrates coated with the crosslinkable compositions. [Background technology]

[0002] It is generally known that achieving matte is difficult, especially in high-solids (crosslinkable) compositions, because conventional techniques, such as silica-based additives, waxes, or micronized polymeric matting agents, require high loadings of such matting additives to achieve low gloss values. It is generally known that the use of high loadings of silica-based matting agents results in poor resistance to several chemicals and poor coating stability. Therefore, there is a need to improve the formulation stability and mechanical and chemical resistance of low-gloss coatings. Furthermore, achieving consistent matte performance across coating film thickness is often problematic, and handling silica-based gloss-reducing agents is typically cumbersome. Furthermore, the durability and transparency of coatings containing silica-based additives are often suboptimal. Furthermore, it is known that achieving a good matte effect, especially in combination with good performance of other important coating properties, is particularly difficult in coatings cured by actinic radiation. Finally, in base-catalyzed coating systems, the acidic nature of many conventional matting agents can strongly impair the drying performance of the coating. In other two-component systems, these agents can also interfere with the drying performance of the paint.

[0003] The use of polyurea-based compounds as rheological agents in film-forming resins is known in the art. Polyurea compounds can be used as sag control agents. See, for example, U.S. Pat. No. 4,851,294, U.S. Pat. No. 4,311,622, U.S. Pat. No. 2,014,037,8587, or European Patent Application Publication No. 01 92 304. U.S. Pat. No. 2003,018,0539 describes the use of urea crystals as a thixotropic agent in compositions curable using actinic radiation. In all of these compositions, polyurea-based compounds are used to control the rheology of the applied coating, and more specifically, to prevent coating sag. These compounds generally have very small average particle sizes, typically well below 10 μm, and narrow particle size distributions. However, these polyurea particles known in the prior art do not reduce the gloss of the coating composition.

[0004] JP 2629747 describes urea-based organic gloss modifiers in various resin solutions, demonstrating that they can effectively reduce the gloss of coatings resulting from the application of such compositions. Improved paint stability and abrasion resistance are also described. However, the systems presented in JP 2629747 have low nonvolatile content of 15-20% by weight, meaning that such systems have very high volatile organic compound (VOC) content, which is undesirable from an environmental and health perspective. Furthermore, the described urea polymers are prepared from near-stoichiometric amounts of diamine and diisocyanate monomers, resulting in linear, relatively high molecular weight species containing many urea linkages. The molecular weight and number of urea linkages in such systems are difficult to control, resulting in a broad particle size distribution and therefore limited control over the final gloss of matte coating compositions. Furthermore, the lack of control over the particle size distribution results in a high percentage of very large particles with diameters larger than the dry film thickness of the applied coating, resulting in clumping defects in the final coating. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, there is a clear need for compositions that provide a strong, tunable matte effect combined with good chemical and mechanical stability, good film transparency and durability, and that are applicable even at high solids. [Means for solving the problem]

[0006] Surprisingly, the Applicants have now found compounds and new compositions which overcome the above-mentioned problems at least in part, if not completely, by providing a particulate polyurea compound a2) according to claim 1. Thus, a first aspect of the invention is a particulate polyurea compound a2) for reducing the gloss of coatings, which comprises the particulate polyurea compound a2) contains an average of at least 2 and at most 6 urea bonds per molecule (or an average urea bond number of at least 2 and at most 6 urea bonds per molecule), The average particle size of the polyurea compound a2) is 11 to 80 μm, the volume percentage of particles of the particulate polyurea compound a2) having a diameter of less than 10 μm (based on particle size distribution data measured using a laser diffraction device) is less than or equal to 40%, preferably less than 30%, more preferably less than 25%, and the volume percentage of particles of the polyurea product (or polyurea compound a2)) having a diameter of more than 20 μm is greater than or equal to 11%, preferably more than 15%, more preferably more than 25%, most preferably more than 40%, It is related to particulate polyurea compounds a2).

[0007] In the context of this specification, polyurea compound a2) may also be referred to as polyurea product. In the context of this specification, urea linkages may also be referred to as urea groups or urea linkages. In the context of this specification, a molecule is defined as an electrically neutral group of atoms held together by covalent chemical bonds. The volume percentage of particles of a certain diameter (of particulate polyurea compound a2)) is measured by laser diffraction using a Malvern Mastersizer S.

[0008] A second aspect relates to a resin composition A comprising: a film-forming resin a1) comprising at least two functional groups, each functional group having at least one type of functionality and / or at least one functional group having at least two types of functionality; a particulate polyurea compound a2 of the present invention; optionally a dispersant a3); and optionally one or more compounds a4) different from a1), a2) and a3).

[0009] In the context of this specification, the functionality of a functional group refers to the number of single covalent bonds that the functional group can form with another functional group (of a different type or the same type) in a selected type of reactive cure chemistry (i.e., when undergoing a certain type of cure), more specifically, the number of single covalent bonds that the functional group can form (or will form) with another functional group of a different type or the same type. For example, a hydroxyl functional group has a functionality of 1 when reacting with an isocyanate functional group or a carboxylic acid functional group. For example, an acryloyl functional group has a functionality of 1 when reacting with an acid malonate CH via Michael addition, but the same acryloyl functional group has a functionality of 2 when reacting with another acryloyl functional group (of the same type) or another type of ethylenically unsaturated moiety in the presence of a radical initiator or under the influence of actinic radiation.

[0010] In the context of this specification, the term "at least one" refers to one, two, three, or more. In the context of this specification, the term "at least two" refers to two, three, or more.

[0011] It has been surprisingly found that the use of such particulate polyurea compounds a2) and such resin compositions A comprising particulate polyurea compounds a2) makes it possible to obtain crosslinkable coating compositions that, after application and curing, have reduced gloss combined with improved durability and chemical resistance. Resin compositions A are highly suitable for formulating crosslinkable compositions, especially those with low volatile organic components and high solids content. Furthermore, the resulting crosslinked compositions offer good mechanical properties, excellent appearance, and very good stability of the matte effect, depending on the dry film thickness. It is particularly surprising that this crosslinkable composition exhibits a low increase in gloss upon scratching the coating, and that the crosslinkable composition whitens much less upon exposure to water and sunlight (compared to compositions containing conventional matte additives known in the art). Furthermore, it has been found that the polyurea compounds a2) according to the invention do not have a significant negative, or even positive, effect on the tack-free time and have excellent xenon resistance. More particularly, resin composition A containing the polyurea compound according to the present invention can be used in known crosslinkable compositions, such as liquid two-component coating systems, such as two-component polyurethane (2K PU) and real Michael addition (RMA) crosslinkable compositions. Resin composition A containing the polyurea compound a2) according to the present invention can also be used in crosslinkable liquid coating systems, such as UV-curable or other actinic radiation-curable compositions. It has also been found that the polyurea particles in resin composition A do not negatively affect the curing of crosslinkable compositions in liquid two-component coating systems, such as two-component polyurethane (2K PU) and real Michael addition (RMA) curable compositions, and that these crosslinkable compositions are shelf-stable. Furthermore, it has also been found that resin composition A containing polyurea compound a2) facilitates easier formulation of low-gloss coating formulations, for example, for use in wood applications. These coating formulations typically have a low solids content, preferably between 15 and 45%. Such paints for application to wood are typically matte using conventional silica and / or wax gloss reducers and often contain cellulose acetate butyrate (CAB) compounds to impart suitable rheological behavior to the paint.It has been found that resin composition A containing the particulate polyurea compound of the present invention can be applied at lower solids than described without using these CAB additives and still have the required rheological behavior. Furthermore, it has been found that the absence of CAB in the crosslinkable composition of the present invention improves the matting effect and improves the stability of the matting effect depending on the number of layers applied. Furthermore, the particulate urea compound of the present invention improves the matting effect at viewing angles close to the horizontal (i.e., gloss reduction at an angle of 85°) compared to the well-known silica-based matting agents already described in the art.

[0012] Within the context of this specification, matting agents may also be referred to as matting compositions, matting compounds, or matting additives.

[0013] Therefore, a third aspect of the present invention is a resin composition A of the present invention, film-forming resin b) and / or film-forming resin a1'), optionally a crosslinker c), optionally a catalyst d) for catalyzing the reaction of the functional groups of the film-forming resin a1) and / or the film-forming resin b) with the crosslinker c), if present, and / or with the film-forming resin b) and / or with the film-forming resin a1′), optionally a reactivity modifier e), optionally volatile organic compounds f), optionally a reactive diluent g), Optionally, another resin h), optionally another matting composition i) different or the same as the particulate polyurea compound a2), preferably a matting composition i) different from the particulate polyurea compound a2). wherein film-forming resins a1), a1'), and b), and crosslinker c), if present, contain at least two functional groups, each functional group having at least one type of functionality, and / or at least one functional group having at least two types of functionality, and film-forming resin a1), and / or film-forming resin a1'), and / or film-forming resin b), are capable of reacting with film-forming resin b) and / or film-forming resin a1'), and / or crosslinker c), if present, and film-forming resin a1') and film-forming resin b), are different from or the same as film-forming resin a1). Film-forming resin a1') is part of resin composition A', described further below.

[0014] Preferably, the crosslinkable composition is capable of providing a reduced gloss coating when applied at a dry film thickness (DFT) of 50 to 60 μm (measured using a Fischer Permascope MP40E-S) having a gloss measurement at an angle of 60° (determined using a BYK Haze-Gloss Meter) of at most 45 gloss units, preferably at most 30 gloss units, more preferably at most 20 gloss units.

[0015] In a fourth aspect, the present invention relates to a method of coating an article or substrate with a crosslinkable composition according to the invention, and in a fifth aspect, to a substrate coated with the crosslinkable composition according to the invention, wherein the coated substrate has a reduced gloss, having a gloss measurement at an angle of 60° (determined using a BYK Haze-Gloss Meter) of at most 45 gloss units, preferably at most 30 gloss units, more preferably at most 20 gloss units, when applied at a dry film thickness (DFT) of 50 to 60 μm (measured using a Fischer Permascope MP40E-S). One embodiment of the present invention will be described below, but the present invention is not limited thereto. [Invention 1] Particulate polyurea compounds a2) for reducing the gloss of coatings, the volume percentage of particles of the particulate polyurea compound a2) having a diameter of less than 10 μm is less than or equal to 40%, preferably less than 30%, more preferably less than 25%, and the volume percentage of particles of the polyurea product having a diameter of more than 20 μm is greater than or equal to 11%, preferably more than 15%, more preferably more than 25%, most preferably more than 40%, The average particle size of the polyurea compound a2) is 11 to 80 μm, the polyurea compounds a2) contain an average number of urea bonds per molecule of at least 2 and at most 6; Particulate polyurea compound a2). [Invention 2] The particulate polyurea compound a2) according to Invention 1 has a relative particle size distribution width, which is the ratio of the particle size at 90% by volume of the particle size distribution to the particle size at 10% by volume of the particle size distribution, of 1 to 10, preferably 2 to 8, and more preferably 2 to 6. [Invention 3] The particulate polyurea compound a2) according to Invention 1 or 2, wherein the average particle size of the polyurea compound a2) is 15 to 80 μm, preferably 15 to 60 μm, more preferably 19 to 41 μm. [Invention 4] 4. The particulate polyurea compound a2) according to any one of claims 1 to 3, wherein the polyurea compound a2) is formed by reacting a polyisocyanate or an isocyanurate, biuret, or uretdione derivative thereof, or another derivative of a polyisocyanate, with at least one amine, preferably a monoamine. [Invention 5] the polyisocyanate is selected from the group consisting of hexamethylene-1,6-diisocyanate (HMDI), its isocyanurate trimer or biuret, trans-cyclohexylene-1,4-diisocyanate, para- and meta-xylylene diisocyanate, toluene diisocyanate, and mixtures thereof; and / or the amine is a monoamine, a primary amine, preferably an n-aliphatic amine, more preferably an n-alkylamine, such as hexylamine, cyclohexylamine, benzylamine, 3-methoxypropylamine, S-α-methylbenzylamine, 2-phenethylamine, or a mixture thereof; The particulate polyurea compound a2) according to Invention 4. [Invention 6] The particulate polyurea compound a2) according to any one of Inventions 1 to 5, wherein the average number of urea bonds in the polyurea compound a2) per molecule is at least 2 and at most 4.5, preferably at least 2 and at most 4, more preferably at least 2 and at most 3.9, and most preferably at least 3 and at most 3.9. [Invention 7] Film-forming resins a1) including: at least two functional groups, each functional group having at least one type of functionality, and / or at least one functional group having at least two types of functionality, The particulate polyurea compound a2) according to any one of Inventions 1 to 6, optionally a dispersant a3), and optionally one or more compounds a4) different from compounds a1), a2) and a3); Resin composition A comprising: [Invention 8] Resin composition A according to invention 7, wherein the particulate polyurea compound a2) is present in an amount of 3 to 30% by weight, preferably 4 to 20% by weight, more preferably 5 to 15% by weight, based on the total weight of the film-forming resin a1) and the polyurea compound a2). [Invention 9] In light of the total weight of resin composition A, the polyurea compound a2) is present in an amount of 2.5 to 20% by weight, the film-forming resin a1) is present in an amount of 1 to 97.5% by weight, preferably 5 to 97.5% by weight, more preferably 15 to 97.5% by weight, even more preferably 30 to 97.5% by weight, dispersant a3) is present in an amount of 0 to 10% by weight, the compound(s) a4) are present in an amount of 0 to 96.5% by weight, preferably 0 to 92.5% by weight, more preferably 0 to 82.5% by weight, even more preferably 0 to 78% by weight, The sum of the weight percentages does not exceed 100%. Resin composition A according to invention 7 or 8. [Invention 10] The resin composition A according to any one of Inventions 7 to 9, wherein the polyurea compound a2) is prepared in the presence of the film-forming resin a1). [Invention 11] 11. Resin composition A according to any one of inventions 7 to 10, wherein a dispersant a3) is present and is selected from the group consisting of polyesters, polyurethanes, and polyacrylates having pigment-affining anionic, cationic, or non-ionic groups, and high molecular weight block copolymers having basic pigment-affining groups, and combinations thereof. [Invention 12] 12. Resin composition A according to any one of Inventions 7 to 11, wherein a4) is an organic solvent a4)-1 and / or an additive a4)-2. [Invention 13] 13. Resin composition A according to any one of Inventions 7 to 12, comprising a reactivity modifier e), the reactivity modifier being selected from the group consisting of carboxylic acids, compounds of the general formula R—SH, compounds containing an XH group having a pKa<12, R—OH, β-diketones, β-ketoesters, α-hydroxyketones, and mixtures thereof. [Invention 14] the functional groups of the film-forming resin a1) are selected from the group consisting of hydroxy, primary amine, secondary amine, mercaptan, activated unsaturated C=C moiety, carboxylic acid, epoxide, isocyanate, activated methylene, methine species such as (derivatives of) acetylacetone, acetoacetate or malonate, and mixtures thereof; and / or the film-forming resin a1) is selected from the group consisting of polyester resins, (meth)acrylic resins, polycarbonate resins, polyether resins, polyurethane resins, amino resins, and mixtures and hybrids thereof; Resin composition A according to any one of inventions 7 to 13. [Invention 15] A crosslinkable composition comprising the resin composition A according to any one of inventions 7 to 14, film-forming resin b) and / or film-forming resin a1'), optionally a crosslinker c), optionally a catalyst d) for catalyzing the reaction of the functional groups of the film-forming resin a1) and / or the film-forming resin b) with the crosslinker c), if present, and / or with the film-forming resin b) and / or with the film-forming resin a1′), optionally a reactivity modifier e), optionally volatile organic compounds f), optionally a reactive diluent g), optionally, another resin h), and optionally another matting composition i) which is different from or the same as the particulate polyurea compound a2). wherein the film-forming resins a1), a1′), and b), and the crosslinker c), if present, comprise at least two functional groups, each functional group having at least one type of functionality, and / or at least one functional group having at least two types of functionality; the film-forming resin a1) and / or the film-forming resin a1′) and / or the film-forming resin b) are capable of reacting with the film-forming resin b) and / or the film-forming resin a1′) and / or the crosslinker c), if present, The film-forming resin a1′) and the film-forming resin b) are different from or the same as the film-forming resin a1); Crosslinkable composition. [Invention 16] the functional groups of the film-forming resins a1′) and b) are selected from the group consisting of hydroxy, primary amine, secondary amine, mercaptan, activated unsaturated C═C moiety, carboxylic acid, epoxide, isocyanate, activated methylene, methine species such as (derivatives of) acetylacetone, acetoacetate or malonate, and mixtures thereof; and / or the film-forming resins a1′) and b) are selected from the group consisting of polyester resins, (meth)acrylic resins, polycarbonate resins, polyether resins, polyurethane resins, amino resins, and mixtures and hybrids thereof; 16. A crosslinkable composition according to claim 15. [Invention 17] 17. Crosslinkable composition according to invention 15 or 16, wherein the crosslinker c) comprises an oligomeric or polymeric compound having functional groups selected from the group consisting of isocyanate, hydroxy, primary amine, secondary amine, mercaptan, activated unsaturated C=C moiety, carboxylic acid, epoxide, activated methylene, methine species such as (derivatives of) acetylacetone, acetoacetate or malonate, and mixtures thereof. [Invention 18] 18. The crosslinkable composition according to any one of inventions 15 to 17, wherein the amount of polyurea compound a2) is 0.5 to 25% by weight, preferably 4 to 20% by weight, more preferably 4 to 15% by weight, based on the total amount of film-forming resin a1), particulate polyurea compound a2), and, if present, dispersant a3), non-volatile portion of additive a4)-2, crosslinker c), film-forming resin b), film-forming resin a1'), catalyst d), reactivity modifier e), reactive diluent g), resin h), and matting composition i) in the crosslinkable composition. [Invention 19] A method of coating an article or substrate to result in a reduced gloss coating having a gloss measurement at a 60° angle of at most 45 gloss units, preferably at most 30 gloss units, more preferably at most 20 gloss units when applied at a dry film thickness (DFT) of 50 to 60 μm. (i) applying the crosslinkable composition according to any one of Inventions 15 to 18; (ii) curing the applied composition A method comprising: [Invention 20] A substrate coated with the composition according to any one of inventions 15 to 18.

[0016] Embodiments of the present invention will now be described in more detail, and for that purpose reference is made to the accompanying drawing, namely FIG. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is a representation of a particle size distribution showing the volume percent of particles of a particulate polyurea compound according to particle size. DETAILED DESCRIPTION OF THE INVENTION

[0018] Particulate polyurea compound a2) A first aspect of the present invention relates to particulate polyurea compounds a2), which may be used in crosslinkable compositions, which form coatings after application to a substrate and drying.

[0019] The particulate polyurea compound a2) according to the present invention contains an average of at least two and at most six urea bonds per molecule. The particulate polyurea compound a2) according to the present invention can reduce the gloss of coatings. The volume percentage of particles of the particulate polyurea compound having a diameter of less than 10 μm is 40% or less, preferably less than 30%, more preferably less than 25%, and the volume percentage of particles of the polyurea product having a diameter of more than 20 μm is 11% or more, preferably more than 15%, more preferably more than 25%, and most preferably more than 40%. The average particle size of the particulate polyurea compound a2) is in the range of 11 μm to 80 μm.

[0020] In one embodiment, the particulate polyurea compound has an average particle size in the range of 11 μm to 80 μm, preferably 15 μm to 80 μm, more preferably 15 to 60 μm, and most preferably 19 to 41 μm.

[0021] In another embodiment, the particulate polyurea compound a2) has a particle size distribution in which the volume percentage of particles having a diameter smaller than 10 μm is in the range of 0 to 40%, preferably 0 to 30%, more preferably 0 to 25%. The volume percentage of particles having a diameter larger than 20 μm is in the range of 11 to 100%, preferably 15 to 100%, more preferably 25 to 80%, most preferably 40 to 70%.

[0022] Preferably, the particulate polyurea compound a2) is not crosslinked.

[0023] Preferably, the particulate polyurea compound a2) has a weight average molecular weight of 200 to 10,000 daltons, more preferably 280 to 7,500 daltons, even more preferably 380 to 4,500 daltons, and most preferably 380 to 3,000 daltons.

[0024] Preferably, the polyurea compound a2) has a melting point higher than the temperature at which the crosslinkable composition is cured. More preferably, the difference between the melting point of the polyurea compound a2) and the curing temperature of the crosslinkable composition is greater than 10°C, more preferably greater than 20°C, and most preferably greater than 30°C.

[0025] Preferably, the melting point of the polyurea compound a2) is below 250°C, more preferably below 200°C, even more preferably below 150°C, most preferably below 100°C.

[0026] The melting point of the polyurea compound a2) can be measured according to ASTM E324.

[0027] In one embodiment, the volume percentage of particles of the particulate polyurea compound a2) that are greater than twice the dried thickness of the crosslinkable composition applied to the substrate is lower than 10%, preferably lower than 5%, more preferably lower than 1% or 0.5%, and most preferably 0%. In the present application, it has been found that if more than 10% by volume of the particles of the particulate polyurea compound have a diameter greater than twice the thickness of the dried crosslinkable composition (i.e., coating), this causes clumping defects in the coating and therefore leads to a poor coating appearance.

[0028] In another embodiment, the volume percentage of particles of the particulate polyurea compound a2) that is larger than the dried thickness of the crosslinkable composition applied to the substrate is lower than 10%, preferably lower than 5%, more preferably lower than 1% or 0.5%, and most preferably 0%.

[0029] According to the present invention, volume percentage or volume % or volume fraction refers to the volume of particles of a particulate polyurea compound having a certain particle size (or diameter) or particle size range in the particle size distribution relative to the total volume of the particulate polyurea compound. More specifically, volume percentage or volume % or volume fraction refers to the proportion of each particle size class in the entire particle size distribution, calculated as a percentage of the total volume of the particles.

[0030] According to the present invention, particle size distribution means the volume distribution in which the volume percentages are measured in terms of particle size.

[0031] The values ​​described in this invention for volume %, particle size, and particle size distribution are measured by laser diffraction using a Malvern Mastersizer S laser diffraction instrument (see the Examples section for further details regarding the experimental equipment and data processing). This instrument allows for the generation of data that can be interpreted by plotting the cumulative volume percentage relative to the total particle volume (y-axis) versus particle diameter (μm) (x-axis) or using a corresponding table. For example, to measure the volume percentage of particles larger than 20 μm, the volume percentage of particles with a diameter smaller than 20 μm relative to the total volume of all particles was first determined by interpolation. The volume percentage of particles larger than 20 μm is 100 minus the interpolated volume percentage of particles smaller than 20 μm.

[0032] The average particle size of the polyurea compounds is determined as the volume moment mean diameter D[4,3] using a Malvern Mastersizer S laser diffraction instrument.

[0033] The average urea bond number of the non-crosslinked polyurea compound a2) is calculated using the following equation I, assuming a conversion of 100% at a molar ratio of isocyanate groups / total amine groups of 1 for the reaction of 1 mole of polyisocyanate with a mixture of monoamines and diamines: Equation I: Average number of urea bonds in polyurea compound a2) = (average functionality of polyisocyanate) / (number of moles of 1-diamine) provided that the number of moles of diamine is strictly less than 1 (ie, the number of moles of diamine cannot be equal to 1).

[0034] For example, when polyurea compound a2) is prepared from 1 mole of 1,6-hexamethylene diisocyanate having an average functionality of 2 and 2 moles of benzylamine, the average number of urea bonds in polyurea compound a2) is calculated to be 2 / (1-0) = 2. When polyurea compound a2) is prepared from 1 mole of an isocyanurate compound having an average functionality of 3, 0.5 moles of a diamine, and 2 moles of a monoamine, the average number of urea bonds in polyurea compound a2) is calculated to be 3 / (1-0.5) = 6.

[0035] The average number of urea bonds in the polyurea compound a2) per molecule is at least 2 and at most 6, preferably at least 2 and at most 4.5, more preferably at least 2 and at most 4, even more preferably at least 2 and at most 3.9, and most preferably at least 3 and at most 3.9.

[0036] In certain preferred embodiments, the relative particle size distribution width is less than 10, preferably between 1 and 10, more preferably between 1.1 and 10, even more preferably between 2 and 8, and most preferably between 2 and 6. When the particle size distribution width is less than 10, coatings made from crosslinkable compositions comprising the present polyurea compounds a2) have been found to have reduced gloss, with gloss measurements at an angle of 60° (determined using a BYK Haze-Gloss Meter) of less than 45 gloss units when applied at a dry film thickness (DFT) of 50 to 60 μm (measured using a Fischer Permascope MP40E-S).

[0037] The relative particle size distribution width according to the present invention is defined as the ratio of the particle size at 90% by volume of the particle size distribution to the particle size at 10% by volume of the particle size distribution. The relative particle size distribution width is calculated according to Equation II below. Equation II: Relative particle size distribution width = [(particle size at 90% by volume of particle size distribution) / (particle size at 10% by volume of particle size distribution)]

[0038] An example of a particle size distribution curve is shown in Figure 1. Figure 1 is a representation of a particle size distribution showing the volume percent of particles of a particulate polyurea compound according to particle size. The curve shows the particle sizes at 10% and 90% by volume. The particle size distribution width can be measured by dividing the particle sizes at 90% and 10% by volume.

[0039] An example of a measurement of the relative particle size distribution width is that if 90% by volume of the particles in a particle size distribution have a size less than or equal to 50 μm and 10% by volume of the particles have a size less than or equal to 8 μm, then the relative particle size distribution width is 50 / 8=6.25 (see Equation II).

[0040] In one embodiment, the polyurea compound a2) is formed by reacting a polyisocyanate or its isocyanurate, biuret, or uretdione derivative, or other (condensation) derivative (of a polyisocyanate) with at least one amine, preferably a monoamine. In another embodiment, the polyurea compound a2) is formed by reacting a monoisocyanate (including a diisocyanate, one of which is selectively reacted) with a polyamine.

[0041] The use of the prefix "poly" in polyisocyanates and polyamines indicates that at least two of the listed functionalities are present in each polyfunctional compound.

[0042] The polyisocyanate is preferably selected from the group consisting of aliphatic, cycloaliphatic, aralkylene, and arylene polyisocyanates, more preferably substituted or unsubstituted linear aliphatic polyisocyanates (and their isocyanurate, biuret, uretdione, or other (condensation) derivatives) and substituted or unsubstituted aralkylene and cyclohexylene polyisocyanates. Optionally, the polyisocyanate can contain other functional groups, such as, for example, ether, ester, or urethane functionalities.

[0043] The polyisocyanates typically contain 2 to 40, preferably 4 to 15, carbon atoms between the NCO groups. The polyisocyanates preferably contain an average of 2 to 5 isocyanate groups, more preferably an average of 2 to 3.9 isocyanate groups. Even more preferably, symmetrical aliphatic or cyclohexylene diisocyanates or derived isocyanurates are used.

[0044] Suitable examples of diisocyanates are preferably tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene-1,6-diisocyanate (HMDI), octamethylene-1,8-diisocyanate, dodecamethylene-1,12-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, trans-cyclohexylene-1,4-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4′-diisocyanate, 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane (isophorone diisocyanate, IPDI), 1,5-dimethyl-(2,4-[ω]-

[0033] The alkyl methyl isocyanate is selected from the non-limiting group consisting of 1,5-dimethyl(2,4-[ω]-diisocyanatoethyl)benzene, 1,3,5-trimethyl(2,4-[ω]-diisocyanatomethyl)benzene, 1,3,5-triethyl(2,4-[ω]-diisocyanatomethyl)benzene, 1,5-naphthalene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, meta-xylylene diisocyanate, para-xylylene diisocyanate, dicyclohexyl-dimethylmethane-4,4'-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and diphenylmethane-4,4'-diisocyanate (MDI).

[0045] Another suitable polyisocyanate is preferably selected from the group consisting of HMDI-based polyisocyanates, including (condensation) derivatives of HMDI, such as uretdiones, biurets, isocyanurates (trimers), and asymmetric trimers, many of which are commercially available as DESMODUR® N and TOLONATE® HDB and TOLONATE® HDT. Other non-limiting examples of (condensation) derivatives of diisocyanates include methylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 1,5-diisocyanatopentane, isophorone diisocyanate, ω,ω'-dipropyl ether diisocyanate, thiodipropyl diisocyanate, cyclohexyl-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,5-dimethyl-2,4-dimethyl ... ,4-bis-(isocyanatomethyl)-benzene, 1,3,5-trimethyl-2,4-bis-(isocyanatomethyl)benzene, 1,3,5-triethyl-2,4-bis-(isocyanatomethyl)benzene, dicyclohexyldimethylmethane-4,4'-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and diphenylmethane-4,4'-diisocyanate.

[0046] Mixtures of the above isocyanate-functional compounds are also applicable.

[0047] Particularly preferred polyisocyanates are selected from the group consisting of HMDI and its (condensation) derivatives, such as its isocyanurate trimer or its biuret, trans-cyclohexylene-1,4-diisocyanate, para- and meta-xylylene diisocyanate, toluene diisocyanate, and mixtures thereof.

[0048] The most preferred polyisocyanate is HMDI or its (condensation) derivatives, such as isocyanurate derivatives.

[0049] As will be appreciated by those skilled in the art, conventionally blocked polyisocyanates that generate more than one isocyanate in situ can also be used, so long as the blocking agent does not prevent the formation of particulate polyurea compounds a2) after cleavage. Throughout this document, the term "polyisocyanate" is used to refer to all polyisocyanates and polyisocyanate-generating compounds.

[0050] According to a preferred embodiment of the present invention, the amines used to prepare the polyurea compounds a2) comprise monoamines.

[0051] The amine generally contains up to 55 carbon atoms, preferably 1 to 24, and more preferably 1 to 12 carbon atoms. Many monoamines can be used in combination with polyisocyanates to produce polyurea reaction products. Aliphatic and aromatic amines can be used, and primary and secondary amines can be used.

[0052] Preferably, primary amines are used. Of these, n-alkylamines and ether-substituted n-alkylamines are particularly useful according to the present invention. Optionally, the amines may contain other functional groups such as hydroxyl groups, ester groups, and urethane groups. Preferred monoamines include aliphatic amines, particularly alkylamines, such as ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, α-methylbutylamine, α-ethylpropylamine, ethylbutylamine, hexylamine, octylamine, decylamine, dodecylamine, octadecylamine, stearylamine, cyclohexylamine, benzylamine, S-α-methylbenzylamine, 2-phenethylamine, ethanolamine, 6-aminohexanol, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxy-1-propylamine, and 1-methoxymethylpropylamine. amines, 1,1-dimethoxy-2-propylamine, 3-ethoxy-1-propylamine, 3-butoxy-1-propylamine, 3-(2-ethylhexyloxy)-1-propylamine, 3-tridecyloxypropylamine, 3-stearyloxypropylamine, p-methoxybenzylamine, 3,4-dimethoxybenzylamine, p-methoxyphenylethylamine, 3,4-dimethoxyphenyl-ethylamine, 9-phenoxy-4,7-dioxanon-1-amine, furfurylamine, tetrahydrofurfurylamine, 2-(4-morpholinyl)ethylamine, 4-(3-aminopropyl)morpholine, and 2,2′-aminoethoxyethanol, and mixtures thereof.

[0053] Particularly preferred are monoamines which are primary amines, preferably n-aliphatic amines, more preferably n-alkylamines such as hexylamine, cyclohexylamine, benzylamine, 3-methoxypropylamine, S-α-methylbenzylamine, 2-phenethylamine, or mixtures thereof.

[0054] The use of diamines as a component next to the monoamines is also an option. Suitable diamines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminehexane, isophoronediamine, 4,4-diaminodicyclohexylmethane, diphenylmethane-4,4'-diamine, 4,7-dioxadecane-1,10-diamine, 4,9-dioxadecane-1,12-diamine, 7-methyl-4,10-dioxatridecane-1,13-diamine, 4,7,10-trioxatridecane-1,13-diamine, dideoxy-diaminoisoidide, and dideoxy-diaminoisosorbide. In the embodiment in which the polyurea compound a2) is formed from a polyisocyanate and a mixture of monoamines and diamines, the molar ratio of amine groups originating from diamines / amine groups originating from monoamines is preferably less than or equal to 0.8, more preferably less than 0.5, and most preferably less than 0.3.

[0055] Mixtures of the above amines are also applicable.

[0056] The monoamines or a portion of the monoamines used to prepare the polyurea compounds a2) can be chiral monoamines, and the polyurea compounds described in US Pat. No. 8,207,268 are considered to be part of the present invention.

[0057] Particularly preferred polyurea compounds a2) are adducts of (derivatives of) HMDI with benzylamine or S-α-methylbenzylamine or mixtures thereof, and adducts of (derivatives of) HMDI with 3-methoxy-1-propylamine.

[0058] The relative molar ratio of amine to isocyanate is usually 0.7 to 1.3, preferably 0.9 to 1.1, and more preferably 0.95 to 1.05.

[0059] The particulate polyurea compound a2) of the present invention contains an average number of urea bonds per molecule of at least 2 and at most 6. Preferably, the average number of urea bonds (or urea linkages) per polyurea molecule is 2 to 4.5, more preferably 2 to 4, even more preferably 2 to 3.9, and most preferably 3 to 3.9 (more specifically, the average number of urea bonds per polyurea molecule is at least 2 and at most 4.5, preferably at least 2 and at most 4, more preferably at least 2 and at most 3.9, and most preferably at least 3 and at most 3.9). In this way, the average particle size (of the particulate polyurea compound a2)) can be controlled. If the (average) particle size is too large, clumping defects may become visible in the applied coating.

[0060] To obtain particulate polyurea compounds a2) having a volume percentage of less than 40%, preferably less than 30%, and more preferably less than 25% with diameters less than 10 μm and a volume percentage of greater than 11%, preferably greater than 15%, more preferably greater than 25%, and most preferably greater than 40% with diameters greater than 20 μm, the polyurea compounds are generally prepared by stirring or agitating the reactants in any convenient manner, either batchwise or continuously. The stirrer rotation speed is preferably 1-30 m / s, preferably 1-20 m / s, and more preferably 1-10 m / s, at the tip of the stirrer. Preferably, the preparation of polyurea compounds a2) is carried out at temperatures between 0 and 120°C, preferably between 10 and 80°C, and more preferably between 10 and 60°C. Those skilled in the art will recognize that process conditions may vary depending on the vessel used to prepare the polyurea and will understand how to modify the parameters to obtain a particular volume percentage with a particular diameter range.

[0061] Small amounts of co-reactive components may also be intentionally employed in the preparation reaction of polyurea compound a2) to act as crystallization modifiers, more particularly to modify the crystal size or colloidal stability of the resulting crystals upon precipitation. Similarly, dispersants and other adjuvants may be present in any of these introduction steps.

[0062] To prepare the particulate polyurea compound a2), the amine component can be added to the isocyanate or the isocyanate can be added to the amine component, whichever is most convenient. Those skilled in the art can adapt the process conditions (more particularly the order of addition and / or mixing) to control the resulting particle size distribution and average particle size of the polyurea compound.

[0063] For the final composition or any other coating formulation component, the polyurea-forming reaction can be carried out in the presence of an inert solvent, such as an aliphatic hydrocarbon such as acetone, methyl isobutyl ketone, N-methylpyrrolidone, benzene, toluene, xylene, butyl acetate, petroleum ether, alcohol, water, or mixtures thereof, or in the presence of a film-forming resin a1) (see also below), where the term "inert" indicates that the solvent and / or film-forming resin a1) do not significantly interfere with the process of polyurea formation, meaning that the amount of polyurea produced in the presence of the solvent is at least 80% of the amount produced in the absence of the solvent and / or resin.

[0064] Resin composition A As stated, the second aspect of the present invention comprises: Film-forming resins a1) including: at least two functional groups, each functional group having at least one type of functionality, and / or at least one functional group having at least two types of functionality, the particulate polyurea compounds a2) of the present invention, optionally a dispersant a3), and optionally one or more compounds a4) different from a1), a2) and a3); The present invention relates to a resin composition A comprising:

[0065] According to the present invention, a film-forming resin is understood to be a compound that can react, optionally in the presence of a catalyst, with another or the same film-forming resin or with a crosslinker, if present, to form a coating (also called a film). A film-forming resin has at least two functional groups, each functional group having at least one type of functionality, and / or has at least one functional group having at least two types of functionality, and can therefore crosslink with other compounds on at least two sides, forming a crosslinked coating.

[0066] According to a preferred embodiment of the present invention, the particulate polyurea compound a2) is prepared in the presence of the film-forming resin a1). This can be achieved by mixing a mixture of the film-forming resin a1) and an isocyanate with an amine, or by mixing an isocyanate with a mixture of the film-forming resin a1) and an amine component, or by mixing two mixtures of the film-forming resin a1) with the amine component and the NCO component, respectively (i.e., mixing a mixture of the film-forming resin a1) and the amine component with a mixture of the film-forming resin a1) and the NCO component); or by simultaneously mixing the isocyanate and the amine with the film-forming resin a1). The amine component and the isocyanate component can be any of the compounds described above.

[0067] It is self-evident that if the film-forming resin a1) is highly reactive towards amines or isocyanates, the film-forming resin and that particular sensitive compound cannot be premixed, where the term "highly reactive" means that more than 30% of the sensitive amine or isocyanate reacts with the film-forming resin a1) before the amine and isocyanate are mixed to prepare the polyurea compound a2).

[0068] In one embodiment, the concentrations of amine- and isocyanate-functional components in the resin composition A that lead to the formation of the particulate polyurea matting agent (or particulate polyurea compound) a2) are selected so as to obtain a polyurea content of 3 to 30% by weight, preferably 4 to 20% by weight, more preferably 5 to 15% by weight, based on the total weight of the film-forming resin a1) and the polyurea compound a2), in accordance with equation III (see further below).

[0069] According to another embodiment, the particulate polyurea matting agent a2) is present in a content (in an amount of) 3 to 30% by weight, preferably 4 to 20% by weight, more preferably 5 to 15% by weight, relative to the total weight of the film-forming resin a1) and the polyurea compound a2), according to equation III (see below).

[0070] Equation III is defined as the weight percentage of polyurea a2) relative to the total weight of film-forming resin a1) and polyurea compound a2), i.e. Equation III (wt%): Weight % of particulate polyurea compound a2)=[(weight of particulate polyurea compound a2)) / ((weight of film-forming resin a1))+(weight of particulate polyurea compound a2))]×100%

[0071] The amount of polyurea compound a2) in the total resin composition A (thus comprising a1), a2), and optionally a3) and a4)) is preferably at least 2.5 wt. %, more preferably at least 4 wt. % (based on the total weight of resin composition A, the sum of the weight percentages (wt. %) not exceeding 100%).

[0072] In another embodiment, based on the total weight of resin composition A (the sum of the weight percentages (wt%) does not exceed 100%), polyurea compound a2) is present in an amount of 2.5 to 20 wt%, film-forming resin a1) is present in an amount of 1 to 97.5 wt%, preferably 5 to 97.5 wt%, more preferably 15 to 97.5 wt%, and even more preferably 30 to 97.5 wt%, dispersant a3) is present in an amount of 0 to 10 wt%, and one or more compounds a4) are present in an amount of 0 to 96.5 wt%, preferably 0 to 92.5 wt%, more preferably 0 to 82.5 wt%, and even more preferably 0 to 78 wt%.

[0073] The amount of film-forming resin a1) in resin composition A according to the present invention is usually 1 to 97.5% by weight, preferably 5 to 97.5% by weight, more preferably 15 to 97.5% by weight, even more preferably 30 to 97.5% by weight, even more preferably 35 to 80% by weight, and most preferably 35 to 70% by weight, based on the total resin composition A. The amount of film-forming resin a1) is preferably at least 45% by weight, more preferably at least 50% by weight, based on the total resin composition A.

[0074] The amount of dispersant a3) in resin composition A is preferably 0 to 10% by weight, more preferably 0.1 to 8% by weight, and most preferably 0.2 to 7% by weight, based on the total weight of resin composition A.

[0075] Particularly preferred is a resin composition A (the sum of the weight percentages (% by weight) does not exceed 100%) comprising 35 to 80% by weight of a film-forming resin a1), 3 to 15% by weight of a polyurea compound a2), 0 to 7% by weight of a dispersant a3), 20 to 70% by weight of a volatile organic compound (or organic solvent) a4)-1, and 0 to 8% by weight of other compounds (or additives) a4)-2.

[0076] Resin composition A preferably contains less than 10% by weight of water, more preferably less than 5% by weight of water, and most preferably less than 1% by weight of water, or even substantially no water (i.e., no water, so-called non-aqueous composition).

[0077] In one embodiment, the polyurea compound a2) is prepared in situ in the presence of the film-forming resin a1).

[0078] The polyurea compound a2) can also be prepared while preparing the crosslinkable composition (see further). This can be done by dissolving the amine-functional component described above in any of the components of the crosslinkable composition, such as the film-forming resins a1) and / or b) and / or the crosslinker c), and mixing the resulting amine-containing solution with the polyisocyanate described above dissolved separately in another or the same component of the crosslinkable composition. Alternatively, the polyurea compound a2) can be generated in situ by mixing the amine-functional species dissolved in any of the components of the crosslinkable composition, such as the film-forming resins a1) and / or b), with the crosslinker c), whereby the crosslinker c) is the polyisocyanate described below.

[0079] Film-forming resins a1), a1') and b) As will be further stated, the crosslinkable composition according to the invention may comprise another film-forming resin b) or a1') which may be the same as or different from the film-forming resin a1). The film-forming resins a1), a1') and b) are described below.

[0080] The film-forming resin a1') is a part of the resin composition A', which further comprises one or more of a particulate polyurea compound a2'), optionally a dispersant a3'), and optionally a compound a4') different from a1'), a2'), and a3'). If the film-forming resin a1) is capable of reacting with the film-forming resin a1'), the resin composition A' can comprise the same or different composition as the film-forming resin a1'). The film-forming resin a1) may be the same as or different from the film-forming resin a1'). The film-forming resin composition A' and its compounds a1'), a2'), a3'), and a4') are as described throughout this specification for the film-forming resin composition A and its compounds a1), a2), a3), and a4), respectively, mutatis mutandis. Thus, herein, the features, embodiments, and examples described herein for a1) are the same as for a1').

[0081] There are no limitations on the composition of the backbone of the film-forming resins a1) and b). Preferably, the film-forming resin a1) or b) is selected from the group consisting of polyester resins, (meth)acrylic resins, polycarbonate resins, polyether resins, polyurethane resins, amino resins, and mixtures and hybrids thereof. Such polymers are generally known to those skilled in the art and are commercially available.

[0082] The film-forming resin b) can be different from or the same as the film-forming resin a1). The functional group can be any functional group. Preferred functional groups are hydroxy, primary amine, secondary amine, mercaptan, activated unsaturated C=C moiety, carboxylic acid, epoxide, isocyanate, activated methylene, or methine species, such as acetylacetone, acetoacetate, or malonate (or derivatives thereof). More preferred functional groups are hydroxy, primary amine, secondary amine, mercaptan, activated unsaturated C=C moiety, carboxylic acid, epoxide, activated methylene, or methine species, such as acetylacetone, acetoacetate, or malonate (or derivatives thereof). The functional group can be blocked by chemical reaction, for example, ketimine, as a blocked form of a primary amine blocked by a ketone. Those skilled in the art are well aware of such chemical blockers. The film-forming resin a1) or b) can contain more than one type of functional group. These different types of functional groups can be present in the same or different molecules. The functional groups of a1) or b) can be capable of reacting with other functional groups from a1) or b). It is also possible that the functional groups a1) and / or b) can be capable of reacting with the crosslinker c), if present.

[0083] Thus, film-forming resin a1) may be crosslinkable with another film-forming resin a1'), which may be the same as or different from a1); film-forming resin a1) may be crosslinkable with film-forming resin b), which may be the same as or different from a1); and / or film-forming resins a1) and / or a1') may be crosslinkable with crosslinking agent c), if present, and / or film-forming resin b) may be crosslinkable with film-forming resin c).

[0084] Of the wide variety of potentially suitable film-forming resins a1) and b), polyester resins, polyurethane resins and (meth)acrylic resins, amino resins, or mixtures or hybrids thereof are preferred.

[0085] The film-forming resin a1) or b) used in the resin composition A according to the present invention preferably has a weight average molecular weight Mw of less than 30,000 Daltons, more preferably less than 10,000 Daltons, most preferably less than 5,000 Daltons.

[0086] The number average molecular weight Mn of resin a1) or b) is preferably at most 10,000 daltons, more preferably at most 5,000 daltons, most preferably at most 3,000 daltons.

[0087] The polydispersity of the molecular weight distribution of resin a1) or b) is preferably 1 to 10, more preferably 1.5 to 6, and most preferably 1.7 to 4, as determined by dividing the weight average molecular weight Mw by the number average molecular weight Mn.

[0088] The glass transition temperature Tg of the film-forming resin a1) or b) is preferably above −80° C., more preferably above −40° C., and most preferably above −30° C. The glass transition temperature of resin a1) preferably does not exceed 100° C., more preferably 90° C., and most preferably 80° C.

[0089] The film-forming resin a1) or b) has an equivalent weight in the range of 50 to 2500 grams of resin a1) or b) per mole of functional group, preferably in the range of 80 to 400 grams of resin a1) or b) per mole of functional group, and more preferably in the range of 100 to 300 grams of resin a1) or b) per mole of functional group.

[0090] According to a first particularly preferred embodiment of the film-forming resin a1) or b), resin a1) or b) is a polyol. Polyol a1) and b) contain an average of at least two -OH groups, preferably more than two. Preferably, polyol a1) and / or b) contain an average of at least 2.2 -OH groups, more preferably an average of at least 2.5 -OH groups. Polyol b) can comprise the same polyol as polyol a1), and / or polyol b) can comprise a different polyol compared to polyol a1).

[0091] Polyols a1) and b) are preferably selected from the group consisting of polyester polyols, (meth)acrylic polyols, polycarbonate polyols, polyether polyols, polyurethane polyols, and mixtures and hybrids thereof. Such polymers are generally known to those skilled in the art and commercially available. Polyol a1) or b) is preferably selected from the group consisting of polyester polyols and (meth)acrylic polyols, as further described below, and mixtures and hybrids thereof. Of the wide variety of potentially suitable polyols a1) and b), polyester polyols, (meth)acrylic polyols, or hybrids or mixtures thereof are preferred. Suitable polyester polyols can be obtained, for example, by polycondensation of one or more difunctional and / or polyfunctional hydroxy compounds with one or more difunctional and / or polyfunctional carboxylic acids, their C1-C4 alkyl esters, and / or anhydrides, optionally in combination with one or more monofunctional carboxylic acids and / or their C1-C4 alkyl esters and / or monofunctional hydroxy compounds. Non-limiting examples of monocarboxylic acids include linear or branched alkylcarboxylic acids containing 4 to 30 carbon atoms, such as stearic acid, 2-ethylhexanoic acid, and isononanoic acid. Non-limiting examples of difunctional and / or higher functional hydroxy compounds include one or more alcohols selected from the group consisting of ethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, isosorbide, spiroglycol, trimethylolpropane, glycerol, trihydroxyethyl isocyanurate, and pentaerythritol. Non-limiting examples of difunctional and / or higher functional carboxylic acids include one or more alcohols selected from the group consisting of succinic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, hexahydrophthalic acid, terephthalic acid, isophthalic acid, phthalic acid, and functional equivalents thereof. Polyester polyols can be prepared from difunctional and / or higher functional hydroxy compounds and carboxylic acids and / or anhydrides and / or C1-C4 alkyl esters of those acids.

[0092] Typical preferred acid numbers for polyols are less than 15 mg KOH / g, preferably less than 10 mg KOH / g, and most preferably less than 8 mg KOH / g. Acid numbers can be determined according to ISO 3682-1996. Suitable (meth)acrylic polyols can be obtained, for example, by (co)polymerizing a hydroxy-functional (meth)acrylic monomer with another ethylenically unsaturated comonomer in the presence of a radical initiator. Non-limiting examples of (meth)acrylic polyols include residues formed from the polymerization of one or more hydroxyalkyl esters of (meth)acrylic acid, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol esters of (meth)acrylic acid, polypropylene glycol esters of (meth)acrylic acid, and mixed polyethylene glycol and polypropylene glycol esters of (meth)acrylic acid. More preferably, the (meth)acrylic polyols include monomers that do not contain hydroxyl groups, such as methyl (meth)acrylate, tert-butyl (meth)acrylate, isobornyl (meth)acrylate, isobutyl (meth)acrylate, (substituted) cyclohexyl (meth)acrylate, and (meth)acrylic acid. The (meth)acrylic polyols optionally contain non-(meth)acrylate monomers such as styrene, vinyl toluene or other substituted styrene derivatives, vinyl esters of (branched) monocarboxylic acids, maleic acid, fumaric acid, itaconic acid, crotonic acid, and monoalkyl esters of maleic acid.

[0093] According to a second preferred embodiment, the polyol a1) or b) comprises a mixture of more than one polyol a1) or b), as described for the preferred embodiment above, in particular a mixture of at least one (meth)acrylic polyol a1) or b) and at least one polyester polyol a1) or b).

[0094] Polyol a1) or b) can be a so-called hybrid polyacrylate polyester polyol, in which the (meth)acrylic polyol is prepared in situ in the polyester polyol. The (meth)acrylic polyol and polyester polyol are preferably obtained using the same monomers as described above for the (meth)acrylic polyol and polyester polyol.

[0095] According to a third particularly preferred embodiment, the film-forming resin a1) or b) comprises an amino resin, preferably a melamine-formaldehyde resin. Melamine-formaldehyde resins are very well known and have been commercially available for a long time and are available from allnex under the trade names CYMEL® and SETAMINE®. These melamine-amino resins contain products with various degrees of methylolation, etherification or condensation (monocyclic or polycyclic), optionally dissolved in corresponding organic solvents.

[0096] According to a fourth particularly preferred embodiment, the film-forming resin a1) or b) comprises a functionality which is an acidic proton (CH) in an activated methylene or methine group. In this preferred embodiment, the film-forming resin a1) or b) is preferably a malonate or acetoacetate, preferably predominantly malonate, or a mixture thereof. The film-forming resin a1) or b) is preferably one or more polymers selected from the group consisting of polyesters, alkyds, polyurethanes, polyacrylates, epoxy resins, polyamides, and polyvinyl resins, which contain malonate and / or acetoacetate moieties in the backbone, pendants, terminals, or a combination thereof.

[0097] This particular fourth embodiment can react with a compound containing functionality, which is an activated unsaturated C=C moiety, as shown below, in the presence of a catalyst d), typically a base. Such compositions are known as real Michael addition (RMA) crosslinkable compositions and are well known in the art. WO11 / 124663, WO11 / 124664, and WO11 / 124665 describe RMA crosslinkable compositions with latent base catalysts, including carbon dioxide-blocked base catalysts that generate a strong base upon carbon dioxide deblocking in a coating layer. WO14 / 166880 describes RMA crosslinkable compositions with catalysts that do not rely on carbon dioxide deblocking, which are particularly suitable for layers where evaporation is hindered, for example, due to thicker layers. WO13 / 050622, WO13 / 050623, WO13 / 050624, and WO13 / 050574 describe RMA crosslinkable compositions with special pot life and open time modifiers. Further descriptions of RMA crosslinkable compositions are found in WO 16 / 166361, WO 16 / 166381, WO 16 / 166382, and WO 2018 / 005077. The descriptions of various embodiments of RMA crosslinkable compositions in these prior art documents are incorporated herein by reference. In particular, reference is made to the above-identified prior art for detailed descriptions of all components of the RMA crosslinkable composition, their preparation, the amounts used in the RMA crosslinkable composition, and measurement methods and definitions, which descriptions are incorporated herein by reference and are applicable unless otherwise stated herein.

[0098] According to a fifth particularly preferred embodiment, the film-forming resin a1) or b) comprises a functionality which is an activated unsaturated C=C moiety. According to this fifth preferred embodiment, the film-forming resin a1) or b) is a (meth)acryloyl compound, preferably an acryloyl compound. Suitable film-forming resins having ethylenically unsaturated functional groups in which the carbon-carbon double bond is activated by an electron-withdrawing group, such as a carbonyl group at the α-position, are disclosed in US 2,759,913 (column 6, line 35 to column 7, line 45), DE-PS-835,809 (column 3, lines 16-41), US 4,871,822 (lines 2, 14 to column 4, line 14), US 4,602,061 (lines 3, 14 to column 4, line 14), US 4,408,018 (column 2, lines 19-68) and US 4,217,396 (column 1, line 60 to column 2, line 64).

[0099] The film-forming resin a1) or b) according to this fifth preferred embodiment is preferably an acrylate, fumarate, or maleate. Most preferably, such film-forming resin a1) or b) is an unsaturated acryloyl-functional component. The component having an activated unsaturated C=C moiety can be selected from the first preferred group of acrylic acid esters of components containing 2 to 6 hydroxyl groups and 1 to 30 carbon atoms. These esters may optionally contain hydroxyl groups. Particularly preferred examples include trimethylolpropane triacrylate, pentaerythritol triacrylate, and di-trimethylolpropane tetraacrylate. Other suitable compounds can be selected from the group of polyester, polyurethane, polyether, and / or alkyd resins containing pendant activated unsaturated groups. Preferably, other suitable compounds can be selected from the group of polyester, polyurethane, polyether, and / or alkyd resins containing pendant activated unsaturated groups. These include, for example, urethane acrylates obtained by reacting polyisocyanates with hydroxyl-containing acrylic esters, such as hydroxyalkyl esters of acrylic acid, or components prepared by esterifying polyhydroxyl components with less than a stoichiometric amount of acrylic acid; polyether acrylates obtained by esterifying hydroxyl-containing polyethers with acrylic acid; multifunctional acrylates obtained by reacting hydroxyalkyl acrylates with polycarboxylic acids and / or polyamino resins; polyacrylates obtained by reacting acrylic acid with epoxy resins; and polyalkylmaleates obtained by reacting monoalkylmaleate esters with epoxy resins and / or hydroxy-functional oligomers or polymers. Such compounds are very well known and have been commercially available for a long time, and are available from Allnex under the trade name EBECRYL®. In addition to acryloyl esters, a suitable class of components is acrylamide.In addition to the film-forming resin a1) or b) described above, which has (at least) two functional groups, each functional group having at least one type of functionality, film-forming resin a1) or b) can also be used, which has at least one functional group having at least two types of functionality.For example, ethylenically unsaturated comonomers such as esters of (meth)acrylic acid can be used in this fifth preferred embodiment, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol esters of (meth)acrylic acid, polypropylene glycol esters of (meth)acrylic acid, and polyethylene glycol and polypropylene glycol mixed esters of (meth)acrylic acid, methyl (meth)acrylate, tert-butyl (meth)acrylate, isobornyl (meth)acrylate, isobutyl (meth)acrylate, (substituted) cyclohexyl (meth)acrylate, (meth)acrylic acid, etc. Non-(meth)acrylate ethylenically unsaturated comonomers such as styrene, vinyl toluene or other substituted styrene derivatives, vinyl esters of (branched) monocarboxylic acids, maleic acid, fumaric acid, itaconic acid, crotonic acid and monoalkyl esters of maleic acid may also be used.

[0100] Optional dispersant a3) Resin composition A also optionally comprises a dispersant a3). Dispersants are generally known in the art and commercially available. Dispersant a3) can be any type of dispersant known in the art.

[0101] In one embodiment, dispersant a3) is present and is selected from the group consisting of polyesters, polyurethanes, and polyacrylates with pigment-affining anionic, cationic, or non-ionic groups, and high molecular weight block copolymers with basic pigment-affining groups. Combinations of dispersants can also be used.

[0102] Compounds suitable for use as dispersants a3) can be selected, for example, from the group of polyurethane dispersants presenting an essentially linear backbone and side chains to which solvent-soluble polyester, polyacrylic, polyether, or polyolefin side chains (including mixtures of such side chains) are laterally attached. Such polyurethane dispersants can optionally be functionalized with reactive carbon-carbon double bonds. Polyurethane dispersants can also be obtained by reacting polyisocyanates with, for example, (cyclic) amine groups, polyesters, and / or polyethers. Polyesters obtainable by reacting fatty acids with hydroxy-C4-5-alkylenecarboxylic acids or lactones can also be used as dispersants. Another class of suitable dispersants includes polyesteramine dispersants, which can be derived from amine-functional species to which polyester chains are attached. The polyester chains can be derived from 12-hydroxystearic acid or from two or more different hydroxycarboxylic acids. Such polyesteramine dispersants can be obtained by reacting polyesters from hydroxycarboxylic acids with diamines. The dispersing resins can also contain one or several polyether chains. Alternatively, such polyesteramine dispersants consist of polyethyleneimine (PEI)-based compounds characterized by a "grafting from" method that allows for the preparation of solvent-based dispersant systems.Polyethyleneimine (PEI)-based pigment dispersants can be represented by the formula X-(T)mP-(T)nH, where P is the polyethyleneimine (PEI) backbone, T is the residue -CO-AO-, A is a C2-C12 alkylene optionally substituted with a C1-C6 alkyl, with the proviso that each linkage between P and T is an amide bond and each linkage between X and T is an ester bond, X is a modifier or terminator residue R-CO-, where R is an unsaturated fatty acid residue, hydroxycarboxylic acid residue, or polyester residue obtained from the polycondensation of a linear or branched, saturated or unsaturated alkanecarboxylic acid or hydroxycarboxylic acid having 1 to 22 carbon atoms, or an acid-terminated polyether, and n, m are independently numbers from 1 to 100. Dendritic molecules can also be applied as dispersants, said dendrimers comprising a functional group reacted with a functional moiety, said moiety being defined as RX, where X is a pigment affinity group and R is a linking moiety chain having at least two atoms in the chain, provided that the functional group and the pigment affinity group are different.

[0103] Suitable dispersants are available from allnex, Altana, and Evonik, among others, and include, but are not limited to, polyesters, polyurethanes, or polyacrylates with pigment-affining anionic, cationic, or nonionic groups, or high molecular weight block copolymers with basic pigment-affining groups, or combinations thereof. Suitable examples include ADDITOL® XL 6577, ADDITOL® VXW 6208 / 60, ADDITOL® XL 6521, ADDITOL® VXW 6208 / 60, and DISPERBYK® 2150.

[0104] It has been found that the addition of a dispersant to the resin composition A according to the present invention results in a decrease in viscosity, which can be beneficial for obtaining low VOC coatings. Low viscosity can also help to obtain good leveling and appearance when used, for example, in spray applications.

[0105] Optionally, one or more compounds a4) different from a1), a2) and a3). The resin composition A according to the invention may optionally comprise one or more other compounds a4) different from a1), a2) and a3).

[0106] In one embodiment, the one or more other compounds a4) are organic solvents (further designated a4)-1) and / or additives (further designated a4)-2).

[0107] The organic compounds can be, for example, volatile organic compounds. Generally, these are compounds with a boiling point at atmospheric pressure of 190° C. or less. Preferably, the amount of volatile organic compounds a4)-1 relative to the total resin composition A is less than 60%, more preferably less than 50%, and most preferably less than 40%. In some embodiments, the amount of volatile organic solvents a4)-1 relative to the total mass of resin composition A can be less than 30%, or even less than 20%.

[0108] Examples of suitable volatile organic compounds a4)-1 include hydrocarbons or their mixtures, such as toluene, xylene, Solvesso 100, Solvesso 150, ketones, terpenes, such as dipentene or pine oil; halogenated hydrocarbons, such as dichloromethane; ethers, such as ethylene glycol dimethyl ether, dipropylene glycol methyl ether; esters, such as ethyl acetate, ethyl propionate, n-propyl acetate, n-butyl acetate, hexyl acetate; ether esters, such as methoxypropyl acetate, butyl glycol acetate, and ethoxyethyl propionate; alcohols, such as n-propanol, isopropanol, n-butanol, methoxypropanol, and 2-ethylhexanol.Mixtures of these compounds can also be used. In another embodiment, resin composition A further comprises an additive compound a4)-2 different from a1), a2), a3), and a4)-1. Additives also include auxiliary agents commonly used in coating compositions. Additives a4)-2 are often used in smaller amounts to improve several important coating properties. These additives a4)-2 can contain a volatile fraction, including solvents with a boiling point of 190°C or less at atmospheric pressure, and a nonvolatile fraction. Examples of such additives include surfactants, leveling agents, wetting agents, anticrater agents, defoamers, heat stabilizers, light stabilizers, UV absorbers, antioxidants, and the reactivity modifier e) described below.

[0109] The amount of such compound a4)-2 is usually 0 to 10% by weight, preferably 1 to 8% by weight, most preferably 2 to 7% by weight, based on the total weight of the film-forming resin a1), the polyurea compound a2), and the dispersant a3), the volatile organic compound a4)-1 and the compound a4)-2, if present.

[0110] crosslinkable composition As stated, the third aspect of the present invention relates to a crosslinkable composition comprising the resin composition A described above. The crosslinkable composition further comprises a film-forming resin b) and / or a film-forming resin a1′), and optionally a crosslinker c). The film-forming resins a1), a1′), and b), and the crosslinker c), if present, comprise at least two functional groups, each functional group having at least one type of functionality, and / or at least one functional group having at least two types of functionality. The film-forming resin a1) and / or the film-forming resin b) can react with the film-forming resin b) and / or the film-forming resin a1′) and / or the crosslinker c), if present. The film-forming resin a1′) and the film-forming resin b) can be different from or the same as the film-forming resin a1). Thus, the film-forming resin a1) can react with the crosslinker c), if present, and / or with the film-forming resin b) and / or the film-forming resin a1′). The film-forming resin b) may also react with the crosslinker c), if present, and / or with the film-forming resin a1') and / or with the film-forming resin b). The film-forming resin a1') may also react with the crosslinker c), if present, and / or with the film-forming resin b) and / or with the film-forming resin a1').

[0111] The crosslinkable composition according to the present invention can optionally further comprise: (d) a catalyst for catalyzing the reaction of the functional groups of the film-forming resin a1) and / or the film-forming resin b) with the crosslinker c), if present, and / or with the film-forming resin b) and / or the film-forming resin a1′); optionally a reactive modifier e); optionally a volatile organic compound f); optionally a reactive diluent g), optionally another resin h), and optionally another matte composition i), which is different from or the same as the particulate polyurea compound a2). Preferably, the reactive diluent g) is different from the film-forming resin b). Preferably, the matte composition i) is different from the particulate polyurea compound a2).

[0112] Preferably, the crosslinkable composition has a solids content of at least 20% by weight, preferably more than 30% by weight, more preferably more than 40% by weight, even more preferably more than 50% by weight, based on the total weight of the composition. In one embodiment, the particulate polyurea compound a2), when used in a crosslinkable composition, is present in the film-forming resin A in an amount such that the amount of particulate polyurea compound a2) in the crosslinkable composition is 0.5 to 25% by weight, preferably 4 to 20% by weight, and more preferably 4 to 15% by weight, based on the total amount of film-forming resin a1), particulate polyurea compound a2), as well as dispersant a3), non-volatile portion of additive a4)-2, crosslinker c), film-forming resin b), film-forming resin a1′), catalyst d), reactivity modifier e), reactive diluent g), other resin h), and matting composition i), if present, in the crosslinkable composition, according to Equation IV. Equation IV (wt%): Weight % of particulate polyurea compound a2) in the crosslinkable composition = [(weight of particulate polyurea compound a2)) / (weight of film-forming resin a1) + weight of particulate polyurea compound a2) + weight of dispersant a3) + non-volatile portion of additive a4)-2 + weight of crosslinker c) + weight of film-forming resin b) + weight of film-forming resin a1') + weight of catalyst d) + weight of reactivity modifier e) + weight of reactive diluent g) + weight of other resin h) + weight of matte composition i))] × 100%

[0113] In this equation IV, the weight percentage of the volatile organic compounds f) and a4)-1 and the volatile portion of additive a4)-2, if any, is not taken into account.

[0114] The amount of resin composition A used in the crosslinkable composition is usually 5 to 99% by weight, preferably 5 to 80% by weight, and most preferably 10 to 75% by weight of the entire crosslinkable composition.

[0115] The non-volatile content of the crosslinkable composition according to the invention at the application viscosity, commonly referred to as the solids content, is preferably at least 20% by weight, more preferably greater than 30% by weight, and most preferably greater than 35% by weight, based on the total crosslinkable composition, where the solids content is calculated according to equation V. Equation V: Solid content [wt %] = {[weight of film-forming resin a1) + weight of polyurea compound a2) + weight of dispersant a3) + weight of non-volatile portions of additives a4)-2 + weight of film-forming resin b) + weight of crosslinking agent c) + weight of film-forming resin a1') + weight of catalyst d) + weight of reactivity modifier e) + weight of reactive diluent g) + weight of binder h) + weight of matting agent i) other than a2) + weight of non-volatile portions of (other) additives)] / [total weight of crosslinkable composition at application viscosity - weight of pigment - weight of filler]} x 100

[0116] Preferably, the crosslinkable composition according to the present invention is an all-solid crosslinkable composition comprising the film-forming resin a1), the polyurea compound a2), the optional film-forming resin a1′), the optional dispersant a3), a1), a1′), a2), and other optional non-volatile compounds a4)-2 different from a3), the optional film-forming resin b), the optional crosslinking agent c), the optional catalyst d), the optional reactivity modifier e), the optional reactive diluent g), the optional other binder h), and the optional matting composition i), 0.5 to 25% by weight, preferably 4 to 20% by weight, more preferably 4 to 15% by weight of a particulate polyurea compound a2), 0.5 to 99% by weight, preferably 5 to 99% by weight, more preferably 10 to 95% by weight, and even more preferably 20 to 90% by weight of film-forming resin a1) + film-forming resin b) + film-forming resin a1') (or 0.5 to 99% by weight, preferably 5 to 99% by weight, more preferably 10 to 95% by weight, and even more preferably 20 to 90% by weight of film-forming resin a1) + b) + a1')), 0 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight of dispersant a3), 0 to 95% by weight, preferably 10 to 80% by weight, more preferably 15 to 50% by weight of a crosslinker c), 0 to 10% by weight, preferably 0.001 to 5% by weight, more preferably 0.005 to 2% by weight of catalyst d), 0 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.2 to 7% by weight of a reactivity regulator e), 0 to 70% by weight, preferably 0 to 50% by weight, more preferably 0 to 20% by weight of a reactive diluent g), 0 to 50% by weight, preferably 0 to 30% by weight, more preferably 0 to 20% by weight of another resin h), 0 to 25% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight of another matting composition i), which is different from or the same as the particulate polyurea compound a2). (The sum of the weight percentages (wt%) does not exceed 100%). Preferably, the reactive diluent g) is different from the film-forming resin b). Preferably, the matting composition i) is different from the particulate polyurea compound a2).

[0117] The crosslinkable composition preferably comprises resin composition A, film-forming resin b), crosslinking agent c), catalyst d), and reactivity modifier e), if present, in a total amount of which they account for 25 to 100% by weight of the total amount of the coating composition.

[0118] In the crosslinkable composition, the total amount of volatile organic compound f) and volatile organic compound a4)-1 preferably accounts for 0 to 80% by weight, more preferably 0 to 70% by weight, even more preferably 0 to 60% by weight, and most preferably 0 to 50% by weight, based on the total weight of the crosslinkable composition.

[0119] The crosslinkable compositions of the present invention provide coatings with reduced gloss, when applied at a dry film thickness (DFT) of 50-60 μm (measured using a Fischer Permascope MP40E-S), having a gloss measurement at an angle of 60° (determined using a BYK Haze-Gloss Meter) of at most 45 gloss units, preferably at most 30 gloss units, more preferably at most 20 gloss units, improved durability and scratch resistance, good transparency, and provide a well-balanced set of other suitable coating properties such as hardness, chemical resistance, flexibility and durability.

[0120] Crosslinker c) The film-forming resins a1), a1′) and / or b) can optionally react with a crosslinking agent c) (whether stated or not, the film-forming resins a1), a1′) and / or b) can be reacted with a crosslinking agent c) if present in the above crosslinkable composition).

[0121] The crosslinker c) comprises an oligomeric or polymeric compound comprising at least two functional groups, each functional group having at least one type of functionality and / or at least one functional group having at least two types of functionality, the functional group(s) being capable of reacting with the film-forming resins a1), a1′) and / or b). There is no limitation on the type of crosslinker c), and as will be appreciated by those skilled in the art, the functional groups in crosslinker c) will depend greatly on the functional groups present in the film-forming resins a1), a1′) and / or b).

[0122] In one embodiment, the functional groups of the crosslinker c) are preferably selected from the group consisting of isocyanate, hydroxy, primary amine, secondary amine, mercaptan, activated unsaturated C═C moiety, carboxylic acid, epoxide, activated methylene, methine species such as acetylacetone, acetoacetate, or malonate (derivatives), and mixtures thereof. Functional groups can also be blocked by chemical reaction. Those skilled in the art are well aware of such chemical blockers. There is no limitation on the composition of the backbone of the crosslinker c). Preferably, the crosslinker c) is selected from the group consisting of (condensation) derivatives of diisocyanates, such as uretdiones, biurets, isocyanurates (trimers), and asymmetric trimers, polyester resins, (meth)acrylic resins, polycarbonate resins, polyether resins, polyurethane resins, amino resins, and mixtures and hybrids thereof. Such crosslinkers are generally known to those skilled in the art and are commercially available.

[0123] Preferably, the relative amounts of functional groups present in the film-forming resins a1) and / or b) and capable of reacting with crosslinker c) and functional groups in crosslinker c) are selected so that the molar ratio of functional groups in crosslinker c) / total functional groups in film-forming resins a1), a1′) and b) is between 0.5 and 3, preferably between 0.75 and 2 or between 0.8 and 1.8.

[0124] Crosslinker component c) can comprise amino resins such as the melamine-formaldehyde resins that are very well known and have been commercially available for a long time and are available from allnex under the trade names CYMEL® and SETAMINE®. These melamine-formaldehyde resins contain products with various degrees of methylolation, etherification or condensation (monocyclic or polycyclic), optionally dissolved in corresponding organic solvents.

[0125] The crosslinker component c) can also include an isocyanate compound, preferably having at least two free -NCO (isocyanate) groups. Isocyanate crosslinkers are well known and have been extensively described in the art. The isocyanate compound is typically selected from the group consisting of aliphatic, cycloaliphatic, and / or aromatic polyisocyanates containing at least two -NCO groups, and mixtures thereof. The crosslinking agent c) is then preferably hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,2-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylene diisocyanatomethane, 3,3'-dimethyl-4,4'-dicyclohexylene diisocyanatomethane, norbornane diisocyanate, m- and p-phenylene diisocyanate, 1,3- and 1,4-bis(isocyanatomethyl)benzene, xylylene diisocyanate, α,α,α'

[0023] Other preferred isocyanate crosslinkers are selected from the group consisting of diisocyanate (condensation) derivatives such as biurets, isocyanurates, imino-oxadiazinediones, allophanates, uretdiones, and mixtures thereof.Examples of such adducts include an adduct of two molecules of hexamethylene diisocyanate or isophorone diisocyanate with a diol such as ethylene glycol, an adduct of three molecules of hexamethylene diisocyanate with one molecule of water, an adduct of one molecule of trimethylolpropane with three molecules of isophorone diisocyanate, an adduct of one molecule of pentaerythritol with four molecules of toluene diisocyanate, an isocyanurate of hexamethylene diisocyanate (available, for example, under the trade names DESMODUR® (E) N3390, TOLONATE® HDT-LV, TOLONATE® HDT-90 or DESMODUR® ultra 2822), a biuret of hexamethylene diisocyanate available under the trade name DESMODUR® N 75, a methyl ... Examples include a mixture of uretdione and isocyanurate of hexamethylene diisocyanate available under the trade name N3400, an allophanate of hexamethylene diisocyanate available under the trade name DESMODUR® LS 2101, and an isocyanurate of isophorone diisocyanate available under the trade name VESTANAT® T1890. Additionally, (co)polymers of isocyanate-functional monomers such as α,α'-dimethyl-m-isopropenylbenzyl isocyanate are suitable for use. If desired, hydrophobically or hydrophilically modified polyisocyanates can also be used to impart specific properties to the coating.

[0126] Crosslinker component c) can also include a blocked isocyanate when a blocking agent with a sufficiently low deblocking temperature can be used to block any of the above polyisocyanate crosslinker components c). In that case, crosslinker component c) is substantially free of compounds containing unblocked isocyanate groups, and the crosslinkable composition can be formulated as a one-component formulation. Blocking agents that can be used to prepare the blocked isocyanate component are well known to those skilled in the art.

[0127] The crosslinker component c) used in the crosslinkable composition can also include polyfunctional amino-functional and / or latent amino-functional compounds. These include polyfunctional species having free primary or secondary amine functional groups, such as aliphatic and cycloaliphatic amines, each having 2 to 10 primary or secondary amino groups and 2 to 100 carbon atoms. Preferred polyfunctional amines contain 2 to 4 primary amino groups and 2 to 20 carbon atoms. Suitable polyfunctional amines include hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-diaminopropane, 1,3-diaminopentane, dodecanediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, para-phenylenediamine, 3-methylpiperidine, piperazine, N-aminoethylpiperazine, isophoronediamine, bis-hexamethylenetriamine, diethylenetriamine, ethylenediamine, dipropylenetriamine, diethylaminetriamine, triethylenetetramine, tris(2-aminoethyl)amine, ethyleneoxide-amine, polyoxyalkyleneamines having 2 to 6 oxyalkylene units, preferably 2 to 4 oxypropylene units, such as those disclosed in U.S. Pat. No. 4,120,839, e.g., JEFFAMINE Examples of suitable curing agents include, but are not limited to, D, ED, and T (JEFFAMINE is a trademark) series polyoxypropylene amines, amine-functional acrylic resins, trimethylhexamethylenediamine, and tetraethylenepentamine. Mixtures of these amine-functional curing agents, as well as adducts of these amine- and epoxy-containing compounds, can also be used, as can polyamidoamines derived from aliphatic polyamines and dimers of unsaturated aliphatic fatty acids. Latent amino-functional compounds, such as moisture-deblockable polyfunctional primary or secondary amine species, preferably ketimines, aldimines, diimines, or oxazolidines, can also be used. These compounds react with water to form free amine groups. Particularly preferred examples include ketimines formed through the condensation reaction of amines and ketones. Examples include the reaction product of a ketone-blocked diethylenetriamine or dipropylenetriamine and an adduct of an epoxy- or isocyanate-containing compound.

[0128] In another embodiment, the crosslinker c) can also contain functionality that is an acidic proton (CH) in an activated methylene or methine group. This embodiment includes the same features as those described in the fourth particularly preferred embodiment of the film-forming resin a1).

[0129] According to another embodiment, the crosslinker c) comprises a functionality that is an activated unsaturated C=C moiety. This embodiment includes the same features as those described for the fifth particularly preferred embodiment of the film-forming resin a1).

[0130] catalyst d) The crosslinkable composition may optionally comprise a catalyst d) for catalyzing the reaction of the functional groups of the film-forming resin a1) and / or the film-forming resin b) with the crosslinker c), if present, and / or with the film-forming resin b) and / or the film-forming resin a1'). Those skilled in the art know that the type of catalyst d) generally depends on the type of functional groups of the film-forming resin a1) and / or the film-forming resin b) and the type of crosslinker component c), if present.

[0131] In one embodiment, catalyst d) is an organic acid, more particularly an organic acid selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, acidic phosphate ester, and mixtures thereof. Sulfonic acid is preferred. Examples of suitable sulfonic acids include dodecylbenzenesulfonic acid (DDBSA), dinonylnaphthalenedisulfonic acid (DNNSA), and para-toluenesulfonic acid (pTSA). The acid catalyst can also be used in a blocked form, resulting in known improvements, such as improved shelf life, of compositions containing the blocked catalyst. Examples of suitable agents for blocking the acid catalyst include amines, preferably tertiary alkylated or heterocyclic amines. The blocked sulfonic acid catalyst can be, for example, blocked DDBSA, blocked DNNSA, or blocked p-TSA. This blocking of the sulfonic acid catalyst can also be achieved, for example, via an amine, preferably a tertiary alkylated or heterocyclic amine, such as 2-amino-2-methylpropanol, diisopropanolamine, dimethyloxazolidine, or trimethylamine. Covalently blocked sulfonic acid catalysts can also be used. In this case, blocking is carried out using a covalent blocking agent, such as an epoxy compound or an epoxy-isocyanate compound. These types of blocked sulfonic acid catalysts are described in detail in U.S. Pat. No. 5,102,961. Catalysts are available, for example, under the trade name CYCAT® (from allnex) or NACURE® and can be used directly in the compositions of the present invention.

[0132] In another embodiment, catalyst d) is a metal-based catalyst. Preferred metals in the metal-based catalyst include tin, bismuth, zinc, zirconium, and aluminum. Preferred metal-based catalysts d) are carboxylate or acetylacetonate complexes of the above metals. Preferred metal-based catalysts d) optionally used in the present invention are tin, bismuth, and zinc carboxylates, more particularly dimethyltin dilaurate, dimethyltin diversatate, dimethyltin dioleate, dibutyltin dilaurate, dioctyltin dilaurate, and stannous octoate, zinc 2-ethylhexanoate, zinc neodecanoate, bismuth 2-ethylhexanoate, and bismuth neodecanoate. Dialkyltin maleates and dialkyltin acetates are also suitable. Mixtures and combinations of metal-based catalysts, mixtures of (blocked) acid catalysts, and mixtures of metal-based catalysts and (blocked) acid catalysts can also be used.

[0133] In another embodiment, the reaction of the functional groups of film-forming resin a1) and / or film-forming resin b) with crosslinker c), if present, and / or film-forming resin b) and / or film-forming resin a1′) can be most conveniently catalyzed by a base. Any base known in the art is suitable. Some common base catalysts include alkali metal hydroxides, alkali metal alkoxides, quaternary ammonium hydroxides (such as tetraalkylammonium hydroxides), and amine compounds (such as diaza compounds, guanidine compounds, cyclic amidines, pyridines, and amidines, including imidazolines). Suitable catalysts are described, for example, in EP 1 462 501, which is incorporated herein by reference. In this embodiment, catalyst d) is preferably a carbon dioxide-blocked strong base catalyst, more preferably a quaternary alkylammonium bialkylcarbonate or alkylcarbonate (such as those described, for example, in EP 2 556 108). Other suitable catalysts for use in this embodiment are the catalysts consisting of a combination of a tertiary amine and an epoxide as described in EP 0 326 723, or the homogeneous base catalyst d) described in PCT / EP2014 / 056953, which is a salt of a basic anion X- from a compound containing an acidic XH group, where X is N, P, O, S, or C, and the anion X- is capable of reacting with the film-forming resin a1) and / or b) and / or a1') and / or the crosslinker c). Other suitable catalysts for use in this embodiment of the invention are the carbamate-blocked catalysts described, for example, in WO 2018 / 005077.

[0134] Reactivity modifier e) In one embodiment, the crosslinkable composition and / or resin composition A according to the invention comprises at least one reactivity modifier e).

[0135] In one embodiment, the reactive modifier is selected from the group consisting of carboxylic acids, compounds of the general formula R-SH, compounds containing an XH group with a pKa<12, R-OH, β-diketones, β-ketoesters, α-hydroxyketones, and mixtures thereof.

[0136] The reactivity modifier e) can be a pot time extender and / or an open time extender. It can be either a pot time extender or an open time extender, and many different types of pot time extenders and open time extenders are known to those skilled in the art. A pot time extender is a component that extends the time required for the viscosity of the crosslinkable composition to double and / or become so high that it prevents convenient application of the crosslinkable composition. An open time extender is a component that extends the period during which flow of the composition can occur after application of the crosslinkable composition to a substrate, thereby improving the flow and leveling of the composition due to reduced solvent entrapment and resulting in better hardness development. Those skilled in the art also know that the type of reactivity modifier e) generally depends on the type of functional groups present in the film-forming resins a1) and / or b), the type of functional groups present in the crosslinker component c) (if present), and the type of catalyst d) selected for the crosslinkable composition according to the present invention. For example, pot life extenders of the β-diketone, β-ketoester and α-hydroxyketone type are well known.Examples of such compounds include 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, and 5-methyl-2,4-hexanedione. 2,4-octanedione, 5,5-dimenthyl-2,4-hexanedione, 3-ethyl-2,4-pentanedione, 2,4-decanedione, 2,2-dimethyl-3,5-nonanedione, 3-methyl-2,4-pentanedione, 2,4-tridecanedione, 1-1-cyclohexyl-1,3-butanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-cyclohexanedione, 1-phenyl-1,3-butanedione, 1(4-biphenyl)-1,3-butanedione, 1-phenyl-1,3-pentanedione, 3-benzyl-2,4-pentanedione, 1-phenyl-5,5-dimethyl-2,4-hexanedione, 1-phenyl-2-butyl-1,3-butanedione , 1-phenyl-3-(2-methoxyphenyl)-1,3-propanedione, 1-(4-nitrophenyl)-1,3-butanedione, 1-(2-furyl)-1,3-butanedione, 1-(tetrahydro-2-furyl)-1,3-butanedione, dibenzoylmethane, methyl acetoacetate, ethyl acetoacetate, α-methyl ethyl acetoacetate, α-n-butyl ethyl acetoacetate, α-sec-butyl ethyl acetoacetate, α-ethyl methyl acetoacetate, and α-ethyl ethyl acetoacetate, α-acetyl-butyrolactone, dimedone, and 1-hydroxyanthraquinone, benzoin, acetoin, and α-hydroxyacetophenone. A particularly preferred pot life extender compound of this class is 2,4-pentanedione.

[0137] Another class of reactivity modifiers e) that are particularly useful in the crosslinkable compositions according to the invention are carboxylic acids, preferably monofunctional carboxylic acids, such as acetic acid, butyric acid, propionic acid, acrylic acid, methacrylic acid, phenylacetic acid, benzoic acid, p-methylbenzoic acid, p-nitrobenzoic acid, p-chlorobenzoic acid, p-methoxybenzoic acid, isononanoic acid, 2-ethylhexanoic acid, pentanoic acid, 3-methylbutanoic acid, neodecanoic acid, versatic acid, 3-hydroxy-2,2-dimethylpropionic acid, 2,2-bis(hydroxymethyl)propionic acid, abietic acid, 1-methylcyclohexanoic acid, dimethylmalonic acid, ethylmethylmalonic acid, diethylmalonic acid, 2,2-dimethylsuccinic acid, 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2,2-dimethylpropionic acid, 2,2-dimethylbutyric acid, 2-ethyl-2 2,2-Dimethylbutyric acid, 2,2-Diethylbutyric acid, 2,2-Dimethylvaleric acid, 2-Ethyl-2-methylvaleric acid, 2,2-Diethylvaleric acid, 2,2-Dimethylhexanoic acid, 2,2-Diethylhexanoic acid, 2,2-Dimethyloctanoic acid, 2-Ethyl-2,5-dimethylhexanoic acid, 3-Methylisocitric acid, 4,4-Dimethylaconitic acid, 1-Methylcyclopentanecarboxylic acid, 1,2,2-Trimethyl-1,3-cyclopentanedicarboxylic acid, 1-Methylcyclohexanecarboxylic acid, 2-Methylbicyclo[2.2.1]-5-heptene-2-carboxylic acid, 2-Methyl-7-oxabicyclo[2.2.1]-5-heptene-2-carboxylic acid, 1-Adamantanecarboxylic acid, Bicyclo[2.2.1]heptane-1-carboxylic acid and Bicyclo[2.2.2]octane-1-carboxylic acid or mixtures thereof. Preferred are acetic acid, propionic acid, isononanoic acid, benzoic acid or tertiary acids, or mixtures thereof.

[0138] Another type of reactive modifier e) particularly useful in the crosslinkable composition according to the invention is a compound of the general formula R-SH, where R can be an alkyl, alkenyl, aryl or aralkyl group. The -SH group can be a primary, secondary or tertiary -SH group. R can be a linear, cyclic or branched group and can contain one or more other functional groups, such as, for example, hydroxyl groups, primary, secondary or tertiary amine groups, silane or siloxane groups, ether groups, ester groups, carboxylic acid groups, etc. Preferably, R has the general formula -C n H 2n+1 [wherein n is 4 to 40, more preferably 8 to 30]. For example, nC 12 H 25 SH, nC 16 H 33 SH, formula C 11 H 23 S.H., C. 12 H 25 SH and C 13 H 27 The present invention includes linear or branched molecules of SH, as well as mixtures thereof, and (CH3)2(iPr)CC(CH3)2-C(CH3)2SH. When R contains more than one type of other functional group, these may be different or the same. In particular, hydroxyl or ester groups are preferred as other functional groups. When R contains an ester group, R is preferably of the general formula -(CH2) n The formula is (C=O)O-R', where n can be selected from the range of 1 to 20, preferably from 1 to 10, and particularly preferably n is 1 or 2. R' can be any alkyl, alkenyl, aryl or aralkyl group, preferably containing 1 to 24 carbon atoms, such as butyl, 2-ethylhexyl, iso-octyl, tridecyl, octadecyl, etc. The formula is HS-(CH2) n Complexing agents of the formula (C=O)O-R', where n is 1 or 2 and R' is an alkyl group containing from 3 to 20 carbon atoms, are particularly preferred.

[0139] When selected from the R-SH type, the reactive modifier e) can contain multiple -SH groups.x -SH compounds [wherein x=1 to 20], compounds of the formula (HSCH2) 4-m C(CH2SCH2CH2SH) m

[0033] where m=1 to 4, and similar compounds described, for example, in patents EP 0665219 and EP 0435306 are preferred. Other particularly preferred pot life / open time extenders e) are esters of SH-functional acids, especially SH-functional carboxylic acids, with polyols. While not necessarily limited to condensation reaction synthesis, such products can be prepared, for example, by the synthesis of HS(CH2) n It can be obtained by forming a (poly)ester bond between COOH (where n=1-20) and a polyol. Formula HS(CH2) n Preferred are reaction products of COOH carboxylic acids (where n is 1 to 20) with polyols having two or more OH-functionalities. In this case, the polyol usually has two or more OH-functionalities and can be a monomer, oligomer, or polymer. Non-limiting examples of such polyols include glycol, glycerol, trimethylolpropane, neopentyl glycol, pentaerythritol, dipentaerythritol, ethoxylated trimethylolpropane, tri(hydroxyethyl)isocyanurate, castor oil, OH-functional polyesters, OH-functional polyacrylates, polycaprolactones, OH-functional polycarbonates, and polymers based on diepisulfide monomers, as described in US Pat. No. 6,486,298.

[0140] Another type of reactivity modifier e) particularly useful in the crosslinkable composition according to the invention is a compound of the general formula R—OH, where R can be an alkyl, alkenyl, aryl or aralkyl group. Furthermore, R can be a linear, cyclic or branched group and can contain one or more other functional groups, such as, for example, an ether or ester group. R—OH is preferably a primary alcohol, more preferably a monoalcohol having 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms, and is preferably selected from the group consisting of ethanol, n-propanol, n-butanol, n-amyl alcohol and butyl glycol.

[0141] Another class of reactive modifiers e) particularly useful in the crosslinkable compositions according to the invention are compounds comprising an XH group, where X is C, N, P, O, or S. The component comprising an XH, preferably an NH group, preferably has a pKa (defined in an aqueous environment) of less than 12, more preferably less than 11, and most preferably less than 10, and preferably greater than 7, more preferably greater than 8, more preferably greater than 8.5. The reactive modifiers e) comprising XH preferably comprise a molecule comprising NH as part of a -(C=O)-NH-(C=O)- group or a -NH-(O=S=O)- group, or a heterocycle in which the nitrogen of the NH group is contained in the heterocyclic ring, preferably selected from a substituted or unsubstituted succinimide, glutarimide, hydantoin, triazole, pyrazole, imidazole, or uracil group, preferably selected from succinimide, benzotriazole, and triazole groups or mixtures thereof.

[0142] Another type of reactive modifier e) particularly useful in the crosslinkable composition according to the present invention is a photochemical initiator capable of initiating polymerization of the actinic radiation-curable polymer composition under UV light. Photochemical initiators (also called photoinitiators) are compounds capable of generating radicals upon absorption of light, typically UV light. The amount of photoinitiator in such a radiation-curable composition is preferably 0.1 to 10 wt %, more preferably 0.5 to 5 wt %, based on the total weight of the radiation-curable composition. The radiation-curable composition may also contain 0 to 5 wt % of one or more photosensitizers well known in the art. Alternatively, the composition may be cured in the absence of an initiator, particularly by electron beam irradiation. Examples of suitable photoinitiators include α-hydroxyketones, α-aminoketones, benzyl dimethyl ketals, acylphosphines, benzophenone derivatives, thioxanthones, and mixtures thereof. Preferably, suitable photoinitiators are selected from the group consisting of α-hydroxyketones, benzophenones, acylphosphines, and mixtures thereof.

[0143] Mixtures of different types of reactive modifiers e) can be used, such as mixtures of carboxylic acids and compounds described by the formula R-SH or mixtures of primary alcohols R-OH and compounds described by the formula XH.

[0144] Remainder of the crosslinkable composition The crosslinkable composition according to the present invention may optionally comprise one or more volatile organic compounds f). The volatile organic compounds f) have the same properties as those described above under a4)-1. Suitable volatile organic compounds f) may be selected from those described above under a4)-1. The properties of such volatile organic compounds f) may be the same or different from those used in resin composition A. Typically, the composition according to the present invention can be diluted with such volatile organic compounds to an application viscosity. The application viscosity can be determined using a rheometer according to ASTM D4287. Generally, the amount of volatile organic compounds a4)-1+f) present in the composition is determined at a shear rate of 1000 s, measured at 25°C. -120 to 20,000 mPa.s, preferably at a shear rate of 1,000 s -1 20 to 10,000 mPa.s, more preferably a shear rate of 1,000 s -1 at a shear rate of 40 to 5000 mPa.s, and even more preferably at a shear rate of 1000 s -1 Preferably, the coating composition according to the present invention comprises less than 700 g / L of volatile organic compounds a4)-1+f) based on the total composition at application viscosity, preferably less than 650 g / L, more preferably less than 600 g / L, more preferably less than 500 g / L, and most preferably less than 400 g / L.

[0145] The resin composition A or crosslinkable composition according to the present invention may also contain a reactive diluent g). Reactive diluents are generally liquid compounds, either monomeric or oligomeric, containing at least one functional group with at least one type of functionality. The type of functional group may be the same as the functional groups present in the film-forming resins a1), a1′), and / or b). The reactive diluent g) is used to reduce the viscosity of the overall crosslinkable composition and can react with the crosslinker c), if present, and with the film-forming resins a1), a1′), and / or b), preferably different from the film-forming resin b). Preferably, the reactive diluent is not volatile (having a boiling point above 190°C at atmospheric pressure) and therefore does not contribute to the overall volatile organic content of the composition.

[0146] In addition to the above components, other compounds may be present in the crosslinkable composition according to the invention. Such compounds may be binder resins h) other than the film-forming resins a1), a1'), or b), optionally containing functionality that can be crosslinked with the film-forming resins a1) and / or b) and / or crosslinker c) when they are present. Examples of such other compounds are ketone resins and latent amino-functional compounds, such as oxazolidines, ketimines, aldimines, and diimines. These other compounds are known to those skilled in the art and are described, inter alia, in US Pat. No. 5,214,086.

[0147] The crosslinkable composition can also contain other matting agents i) that are different or the same as the particulate polyurea compound a2). Examples of such matting agents i) include inorganic matting additives, waxes, or finely divided polymeric matting agents. The inorganic matting agents i), particularly inorganic oxides, are selected from the group consisting of SiO2, Al2O3, AlPO4, MgO, TiO2, ZrO2, Fe2O3, and mixtures thereof. The oxides can be in various forms, including gelled, precipitated, fumed, colloidal, etc. Inorganic oxides can also include natural minerals, processed / activated minerals, montmorillonite, attapulgite, bentonite, diatomaceous earth, silica sand, limestone, kaolin, ball clay, talc, pyrophyllite, perlite, sodium silicate, sodium aluminum silicate, magnesium silicate, magnesium aluminum silicate, silica hydrogel, silica gel, fumed silica, precipitated silica, dialysis silica, alumina zeolite, molecular sieves, diatomaceous earth, reversed-phase silica, bleached clay, and mixtures thereof. Silica-based matting agents i) can be optionally treated with waxes, polymers, or inorganic materials. Waxes used as matting agents i) can be based on polyethylene, polypropylene, carnauba, polytetrafluoroethylene (PTFE), fatty acid-based compounds such as stearates, including zinc stearate, and amides. Micronized polymeric matting agents i) are often based on high molecular weight polymethylurea resins. Furthermore, wax-like micronized polymers based on glucose, starch or other renewable materials can likewise be used as matting agents i).

[0148] The crosslinkable composition may also contain at least one radical inhibitor. Examples of suitable radical inhibitors include hydroquinone (HQ), methylhydroquinone (THQ), tert-butylhydroquinone (TBHQ), di-tert-butylhydroquinone (DTBHQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-tert-butyl-4-methylphenol (BHT), and the like. Other examples of suitable inhibitors include phosphines such as triphenylphosphine (TPP) and tris-nonylphenylphosphite (TNPP), phenothiazine (PTZ), triphenylantimony (TPS), and mixtures of any of these. The total amount of inhibitor used is generally 0 to 1% by weight of the crosslinkable composition, preferably 0.01 to 0.5% by weight, and most preferably 0.01 to 0.1% by weight.

[0149] The crosslinkable composition may further contain other materials, additives, or adjuvants commonly used in coating compositions. These may include additives commonly used in smaller amounts to improve certain important coating properties. These additives may contain volatile and nonvolatile components, including solvents with a boiling point of 190°C or less at atmospheric pressure. Examples of such additives include surfactants, pigment dispersing aids, rheology modifiers, leveling agents, slip additives, wetting agents, anti-crater agents, defoamers, adhesion promoters, alkoxysilanes, flow modifiers, heat stabilizers, light stabilizers, UV absorbers, flame retardants, water, antioxidants, and mixtures thereof. The viscosity of urea-containing formulations can be effectively modified using commonly used dispersing additives, for example, those with acid or base groups. More specifically, dispersing additives such as ADDITOL® XL 6521, ADDITOL® XL 6583, and DISPERBYK® 2150 may be used. The appearance, texture and feel of the final coating applied using the crosslinkable composition of the present invention can be effectively modified using various types of flow and leveling and / or wetting and dispersing additives, such as ADDITOL® XL 204, ADDITOL® XL 122, ADDITOL® XL 123N, ADDITOL® XL 6577, BYK® 306, BYK® 307, BYK® 104, BYK® 358N, BYK® 310 or BYK® 315. The total amount of pigments, colorants, inert resins, fillers and / or additives in the crosslinkable composition of the present invention generally does not exceed 60% by weight, preferably does not exceed 40% by weight, compared to the total weight of the crosslinkable composition.

[0150] The crosslinkable composition can also be a pigmented composition. In this case, a pigment and a filler are present in the composition. Pigments are typically solid components with low solubility in the paint medium and are added to the composition to impart color. Pigmented compositions can include one or more inorganic pigments and / or one or more organic pigments. Fillers are also typically solid components with low solubility in the paint medium and are added to the composition to increase the paint volume or improve other paint parameters, such as providing corrosion resistance.

[0151] In one preferred embodiment, the crosslinkable composition comprises at least one film-forming resin a1), comprising a polyester or polyacrylate resin preferably containing hydroxyl functional groups, a polyurea compound a2), optionally a dispersing agent a3), at least one crosslinking agent c), preferably containing isocyanate functional groups, optionally at least one catalyst d), preferably comprising a metal carboxylate salt, more preferably comprising a dialkyltin dicarboxylate, and optionally at least one reactivity modifier e), preferably comprising a carboxylic acid, a compound having the general formula R—SH, or a mixture thereof.

[0152] In another preferred embodiment, the crosslinkable composition comprises at least one film-forming resin a1), preferably comprising a polyester resin containing acidic CH functional groups, a polyurea compound a2), optionally a dispersing agent a3), at least one crosslinking agent c), preferably comprising an activated unsaturated C=C moiety, optionally at least one catalyst d), preferably comprising a base, more preferably comprising a carbon dioxide blocked strong base catalyst, more preferably comprising a quaternary tetraalkylammonium bialkyl carbonate or alkyl carbonate, and optionally at least one reactivity modifier e), preferably comprising a primary alcohol, a compound having the general formula XH or a mixture thereof.

[0153] In another preferred embodiment, the crosslinkable composition comprises at least one film-forming resin a1), preferably comprising a polyester resin containing acidic CH functional groups, at least one film-forming resin a1′), preferably comprising activated unsaturated C═C moieties, a polyurea compound a2), optionally a dispersing agent a3), optionally at least one catalyst d), preferably comprising a base, more preferably comprising a carbon dioxide blocked strong base catalyst, more preferably comprising a quaternary tetraalkylammonium bialkyl carbonate or alkyl carbonate, and optionally at least one reactivity modifier e), preferably comprising a primary alcohol, a compound having the general formula XH or a mixture thereof.

[0154] In another preferred embodiment, the crosslinkable composition comprises at least one film-forming resin a1), preferably comprising activated unsaturated C=C moieties, a polyurea compound a2), optionally a dispersing agent a3), at least one crosslinking agent c), preferably comprising a polyester resin comprising acidic CH functional groups, optionally at least one catalyst d), preferably comprising a base, more preferably comprising a carbon dioxide blocked strong base catalyst, more preferably comprising a quaternary tetraalkylammonium bialkyl carbonate or alkyl carbonate, and optionally at least one reactivity modifier e), preferably comprising a primary alcohol, a compound having the general formula XH or a mixture thereof.

[0155] In another preferred embodiment, the crosslinkable composition comprises at least one film-forming resin a1), preferably comprising activated unsaturated C=C moieties, a polyurea compound a2), optionally a dispersing agent a3), optionally one or more film-forming resins a1'), preferably comprising activated unsaturated C=C moieties, optionally one or more film-forming resins b), preferably comprising activated unsaturated C=C moieties, and optionally at least one reactive modifier e), preferably comprising a photoinitiator.

[0156] The crosslinkable composition may suitably be prepared for one-component compositions by a process comprising mixing resin composition A with film-forming resins a1') and / or b) and / or optionally with crosslinker c) and optionally with catalyst d). Alternatively, the crosslinkable composition may be prepared for two-component compositions by a process comprising mixing resin composition A with optional film-forming resins a1') or b) and catalyst d) to form a binder component, and mixing said binder component with crosslinker c) or film-forming resins a1') or b). Alternatively, if crosslinker c), if present, or film-forming resin a1′) or b) does not readily react with film-forming resin a1) and / or film-forming resin b) at storage temperatures in the absence of catalyst d, for example when crosslinker c) contains activated unsaturated C═C moieties and when film-forming resin a1) and / or b) contains acidic C−H species, the crosslinkable composition may be prepared by mixing resin composition A with optional film-forming resin b) or a1′), crosslinker c), if present, or film-forming resin b) or a1′) and optionally reactivity modifier e) to form a binder component, and mixing said binder component with catalyst d) for a two-component crosslinkable composition.

[0157] Conventionally, when the crosslinker c) is an isocyanate-functional crosslinker and the resin composition comprises a hydroxyl-functional film-forming resin and an isocyanate-functional crosslinker, the crosslinkable composition according to the invention has a limited pot life. The composition can therefore preferably be provided as a multi-component composition, for example a two-component or three-component composition, in which the hydroxyl-functional film-forming resin a1), film-forming resin a1′) and / or film-forming resin b) on the one hand, and the isocyanate-functional crosslinker c) on the other hand, are part of at least two different components. The invention therefore relates to a kit of parts for preparing a crosslinkable composition, the kit of parts comprising two components: i. a binder module comprising a resin composition A comprising at least one hydroxyl-functional film-forming resin a1), optionally a film-forming resin a1'), a particulate polyurea component a2), optionally a dispersant a3), optionally other components a4), and optionally at least one (hydroxyl-functional) film-forming resin b), and optionally at least one catalyst d), and optionally at least one reactivity modifier e); ii. a crosslinker module comprising at least one crosslinker c) comprising an isocyanate group; The present invention also relates to a kit comprising:

[0158] Or a kit of parts, i. a binder module comprising a resin composition A comprising a hydroxyl-functional film-forming resin component a1), optionally a film-forming resin a1'), a particulate polyurea component a2), optionally a dispersant a3), optionally other components a4), and optionally a (hydroxyl-functional) film-forming resin b); ii. a crosslinker module comprising a crosslinker c) comprising an isocyanate group; and iii. A diluent module containing a volatile organic diluent. and optional catalyst d) can be distributed over modules i, ii or iii, at least one of the modules optionally comprising catalyst d).

[0159] If crosslinker c), if present, or film-forming resin b) or a1′), does not readily react with film-forming resin a1) and / or film-forming resin b) at storage temperatures, e.g., if crosslinker c), if present, or film-forming resin b) or a1′), contains a melamine-amino resin and / or a blocked isocyanate group, all components a) through e) may be supplied in one part. If crosslinker c) is not required (and thus crosslinker c) is not present, i.e., in the absence of crosslinker c), and film-forming resin b) or a1′), does not readily react with film-forming resin a1) and / or film-forming resin b) at storage temperatures in the absence of actinic radiation, e.g., if film-forming resin a1) and / or b) and / or a1′), contains activated unsaturated C═C species, all components of resin composition A, b), and e) may also be supplied in one part.

[0160] If the crosslinker c), if present, or the film-forming resin b) or a1′), does not readily react with the film-forming resin a1) and / or the film-forming resin b) in the absence of the catalyst d) at storage temperature, for example, if the crosslinker c), if present, or the film-forming resin b) or a1′), contains activated unsaturated C═C moieties and the film-forming resin a1) and / or b) contains acidic C−H species, all components of the resin compositions A, A′, b), c) and e) can be supplied in one part and the catalyst d) can be supplied in a separate part. In this case, the invention relates to a kit of parts for preparing a crosslinkable composition, comprising: i. a binder module comprising a resin composition A comprising at least one acidic CH and / or unsaturated C=C functional film-forming resin a1), optionally a film-forming resin a1'), a particulate polyurea component a2), optionally a dispersant a3), optionally other components a4), and optionally at least one film-forming resin b), optionally at least one crosslinker comprising an activated unsaturated C=C moiety and / or at least one acidic CH, c), and optionally at least one reactivity modifier e); ii. a catalyst module comprising at least one catalyst d). The present invention relates to a kit comprising:

[0161] The other components of the crosslinkable composition can be distributed across the modules in various ways, as long as the modules exhibit the required storage stability. It is preferred not to combine components of the crosslinkable composition that react with each other during storage in one module. If desired, the components of the coating composition can be distributed across many more modules, for example, four or five modules.

[0162] In a fourth aspect, the present invention provides a method of coating an article or substrate, to provide a reduced gloss coating, when applied at a dry film thickness (DFT) of 50 to 60 μm (as measured using a Fischer Permascope MP40E-S), having a gloss measurement at an angle of 60° (as determined using a BYK Haze-Gloss Meter) of at most 45 gloss units, preferably at most 30 gloss units, more preferably at most 20 gloss units, (i) applying the crosslinkable composition described above, (ii) curing the applied composition The present invention relates to a method comprising:

[0163] In a fifth aspect, the present invention relates to a substrate coated with the crosslinkable composition described above. The applied film thickness after drying of the coating is 30 to 500 μm, preferably 40 to 250 μm, more preferably 40 to 100 μm, and most preferably 50 to 60 μm. The substrate has a reduced gloss coating having a gloss measurement at an angle of 60° (determined using a BYK Haze-Gloss Meter) of at most 45 gloss units, preferably at most 30 gloss units, and more preferably at most 20 gloss units, when applied at a dry film thickness (DFT) of 50 to 60 μm (measured using a Fischer Permascope MP40E-S).

[0164] The substrate can be, for example, metal, such as iron, steel, tinplate, and aluminum, or plastic, wood, glass, synthetic materials, paper, leather, concrete, or another coating layer. The other coating layer can consist of the coating composition of the present invention or can be a different coating composition. The coating compositions of the present invention find particular utility as clearcoats, basecoats, pigmented topcoats, primers, and fillers.

[0165] The crosslinkable compositions according to the present invention are well suited for use as clearcoats or pigmented topcoats, which are essentially free of pigment and transparent to visible light.

[0166] When the crosslinkable composition of the present invention is a clear coat, it is preferably applied to a wooden substrate, which has been optionally pretreated with a sealing layer. When applied directly to a wooden substrate, the clear coat forms the top layer of a monocoat. When the wood has been pretreated with another layer, the clear coat of the present invention forms the top layer of a multi-layer coating.

[0167] Another preferred application of the crosslinkable composition of the present invention is a clearcoat applied over a color- and / or effect-imparting basecoat, where the clearcoat forms the top layer of a multi-layer lacquer coating, such as those typically applied to automobile exteriors. The basecoat may be water-borne or solvent-borne.

[0168] Another preferred embodiment of the crosslinkable composition of the present invention is a clearcoat applied over plastic objects such as plastic furniture, automobile and transportation vehicle parts, toys, and appliances.

[0169] Another preferred embodiment of the crosslinkable composition of the present invention is a clearcoat applied over a concrete substrate, such as a concrete floor or tile.

[0170] Another preferred embodiment of the crosslinkable composition of the present invention is a pigmented topcoat for coating wooden objects, such as furniture, kitchen cabinets, wooden floors, decorative panels, such as those in automobiles or yachts, wooden building elements, optionally pretreated with a sealing layer; coating metal objects, such as furniture, bridges, pipelines, agricultural, construction, and earthmoving equipment, industrial plants or buildings, oil and gas equipment, or ships; coating concrete substrates, such as concrete floors or tiles; and coating plastic objects, such as furniture, automobile and transportation vehicle parts, toys, and electrical appliances. The composition is also suitable for finishing and refinishing automobiles and large transportation vehicles, such as trains, trucks, buses, and airplanes. Generally, the crosslinkable composition of the present invention can be applied by spraying, brushing, drawing, or any other method to transfer the composition to the substrate.

[0171] Accordingly, the present invention also relates to a method for providing a coating on any substrate for any coating application, comprising applying a coating composition according to the present invention to at least a portion of the surface of the object to be coated and curing the applied coating composition, preferably at a temperature ranging from 5 to 180°C. Those skilled in the art will recognize that the curing temperature depends on the type of crosslinker c), if present, and / or the type of film-forming resin a1), and may be carried out, for example, at 5 to 100°C, or more preferably at 10 to 60°C. The coating composition of the present invention may be at least partially curable upon exposure to actinic radiation. Radiation-curable compositions are generally cured by irradiation, typically ultraviolet (UV) radiation, in the presence of a photoinitiator. They can also be cured by electron beam irradiation, allowing the use of compositions without photoinitiators. Radiation curing is preferably achieved by exposure to high-energy radiation, i.e., ultraviolet light or daylight, e.g., light with a wavelength of 172 to 750 nm, or by irradiation with a high-energy electron beam (e-beam, 70 to 300 keV). Various types of actinic radiation can be used, such as ultraviolet (UV) radiation, gamma radiation, and electron beam radiation. A preferred means of radiation curing is UV radiation. According to one embodiment, the UV radiation is UV-A, UV-B, UV-C, and / or UV-V radiation. [Example]

[0172] Methods and Materials Molecular weights and molecular weight distributions were determined by gel permeation chromatography (GPC) using polystyrene standards, more specifically, size-exclusion chromatography, according to ASTM D3593. The size-exclusion device used was an Alliance system consisting of a pump, autosampler, and He degasser (Degasys DG-1210 from Uniflows), equipped with a PLgel 5 μm MIXED-C 600 × 7.5 mm column and a Plgel 5 μm guard column (50 × 7.5 mm - Polymer Laboratories). The column oven (Separations Analytical Instruments) was set at 30 °C. Tetrahydrofuran (THF-Extra Dry, Biosolve 206347) + 2% acetic acid (Baker 6052) was used as the eluent at a flow rate of 0.8 ml / min. Carbon disulfide (Backer) was used as a marker. A Waters 410 refractive index detector was used. The injection volume was 100 μl at a concentration of 1.5 mg / ml. Polystyrene standards (Polymer Laboratories, Easy PS-1, 2010-0501 (M range 580 g / mol to 8,500,000 g / mol) and Easy PS-2, 2010-0601 (M range 580 g / mol to 400,000 g / mol)) were used to calibrate using a third-order polynomial. Data analysis was performed using Empower (Waters). In the resulting plot of elution weight fraction versus molecular weight, Mn is the molecular weight at which 50% of the molecules eluted, and Mw is the molecular weight at which 50% of the total mass eluted.

[0173] Glass transition temperatures, Tg, were determined according to DEN EN ISO 16805 and ISO 11357 using a Mettler DSC 822E calorimeter. 7-12 mg samples were first heated to 120°C, well above Tg. This temperature was maintained for 5 minutes, after which the temperature was reduced to at least 60°C below the expected Tg in 10 minutes. The samples were then heated to 120°C at a 10°C / min ramp. Tg is the temperature at the intersection of the tangent to the baseline and the tangent with the most negative slope in a heat flow versus temperature plot.

[0174] Hydroxyl number is measured according to ASTM E222-17 method.

[0175] The malonate / acetoacetate active CH equivalents were determined by titrating the malonate / acetoacetate-containing resin with 25 wt% sodium methoxide in methanol. The equivalence point was detected using azo violet indicator solution.

[0176] Volume percent, particle size, and particle size distribution were determined using a Malvern Mastersizer S equipped with a 42-element array detector optimized for light scattering measurements, including a He-Ne laser with a wavelength of 632.8 nm and a beam length of 2.4 mm, and two backscatter detectors. Samples were prepared by diluting 1 gram of film-forming resin containing a polyurea adduct in 9 grams of butyl acetate. The sample was then premixed for 2-3 minutes using a vortex mixer. Measurements were initiated when the obscuration was 10-12.5% ​​and the sample had circulated in the measurement cell for at least 30 seconds. The measurement data were analyzed using a polydispersity analysis model based on Mie theory, assuming a particle refractive index of 1.5330 and a continuous medium refractive index of 1.4000, assuming the particles were completely opaque.

[0177] The tack-free drying time was determined as follows: In an conditioned environment (22°C, 60% relative humidity), a cotton ball was placed on the dried coating, a 1 kg weight was placed on the cotton ball for 10 seconds, the weight was removed, and the cotton ball was blown away. This procedure was repeated depending on the time after the crosslinkable composition was applied. The coating was said to be tack-free when the cotton ball left no visible marks. This time was recorded as the tack-free time.

[0178] Perso hardness was measured in an acclimatization room at 23°C and 55±5% relative humidity. Hardness was measured using a Perso pendulum as described in ASTM D4366.

[0179] Haze and gloss were determined using a BYK Haze-Gloss Meter. Abrasion resistance was determined by scratching the coating 10 times with equal force using 3M281Q WETORDRY™ sandpaper and expressed as the absolute value of the gloss value at 60° before scratching minus the gloss value at 60° after scratching. A lower value means that the coating has good abrasion resistance.

[0180] Xenon resistance was determined according to ISO 11341.

[0181] Dry film thickness (DFT) was measured on metal panels using a Fischer Permascope MP40E-S.

[0182] 0.1s -1 The viscosity at was determined using a cone-plate MCR302 rheometer supplied by Anton-Paar.

[0183] Preparation of Resin 1: A (meth)acrylic polyol having a hydroxyl number of 132 mg KOH / g (based on nonvolatile content), an acid number of 2.4 mg KOH / g (based on nonvolatile content), Mw of 2,867 g / mol, and Mn of 1,303 g / mol (GPC, polystyrene standards), and a Tg of −4° C. was prepared by polymerization of a mixture of acrylic acid, hydroxyethyl methacrylate, butyl acrylate, butyl methacrylate, and styrene. The (meth)acrylic polyol was dissolved in butyl acetate to give a solution with a nonvolatile content of 78% by weight.

[0184] SETALUX® 1915 BA-75 is a 75% acrylic polyol solution in butyl acetate.

[0185] SETALUX® DA 450 BA-50 is a 50% solution of acrylic polyol in butyl acetate.

[0186] ACURE® 510-100 is an 85% solution of a malonate-functional polyester in butyl acetate.

[0187] ACURE® 510-200 is an 85% solution of a malonate-functional polyester in butyl acetate.

[0188] ACURE® 550-105 is an acryloyl-functional oligoester.

[0189] ACURE® 500 is a carbonate-blocked base catalyst (29.5 wt% solids) for the Michael addition reaction.

[0190] DBTL is a dibutyltin dilaurate-based catalyst commercially available under the name TINSTAB® BL 277.

[0191] MBCHA is 4,4'-methylenebis(cyclohexylamine).

[0192] ACEMATT® OK 500 is a precipitated silica that has been post-treated with finely divided wax.

[0193] ACEMATT® 3300 is an advanced polymer treated cyclic silica.

[0194] DEUTERON® PMH-C is a micronized thermosetting polymethylurea.

[0195] CERAFLOUR® 1000 is a finely divided polymer with wax-like properties.

[0196] CERIDUST® 9615A is a micronized blend of polyethylene and amide waxes used to reduce gloss in coatings.

[0197] TOLONATE™ HDT 90 is an aliphatic polyisocyanate based on HDI-trimer (isocyanurate) supplied at 90% solids in a butyl acetate / high flash aromatic solvent blend. The average NCO functionality / trimer molecule is approximately 3.6.

[0198] TOLONATE™ HDT-LV2 is a solvent-free, low-viscosity aliphatic polyisocyanate based on HDI-trimer (isocyanurate). The average NCO functionality per trimer molecule is approximately 3.2.

[0199] DESMODUR® ultra 2822 is an aliphatic polyisocyanate (55% solids) (HDI trimer). The average NCO functionality per trimer molecule is approximately 3.5.

[0200] DESMODUR® N3800 is an aliphatic polyisocyanate (flexibilized HDI trimer) with an average NCO functionality per trimer molecule of approximately 3.8.

[0201] DESMODUR® N 75 MPA / X is an aliphatic polyisocyanate (75% solids) (HDI biuret) used as a curing agent component for polyurethane coating systems.

[0202] IPDI is isophorone diisocyanate.

[0203] ADDITOL® XL 123N is a flow and defoamer based on modified silicone oil.

[0204] ADDITOL® VXL 4951N is a fluoro-modified silicone antifoam agent.

[0205] ADDITOL® XL 6521 is a polymeric wetting and dispersing agent with cationic properties.

[0206] DISPERBYK® 2150 is a high molecular weight wetting and dispersing additive with basic pigment-affinic groups.

[0207] CAB 381-20 is a cellulose acetate butyrate, a cellulose ester with medium butyryl content and high viscosity.

[0208] KRONOS® 2310 is a rutile titanium dioxide pigment.

[0209] In the following examples, the relative particle size distribution width is calculated according to Equation II and is abbreviated in the tables as "(PS at 90% by volume / PS at 10% by volume)". Equation II: Relative particle size distribution width = [(particle size at 90% by volume of particle size distribution) / (particle size at 10% by volume of particle size distribution)]

[0210] In all the examples below, (almost) stoichiometric amounts of isocyanate and amine functionalities were used. Furthermore, the isocyanate-functional species used were trimers based on hexamethylene diisocyanate with an average functionality of 3 to 4 NCO groups per molecule (see above for average functionality values ​​according to the grade of isocyanate trimer used). When such trimer species are reacted with monoamines, the amount of urea groups formed per molecule (or the number of urea bonds or urea linkages formed) corresponds directly to the average functionality of the polyisocyanate grade used according to Equation I. Thus, in the examples below, the average number of urea groups (or the average number of urea bonds or urea linkages) per molecule is 3 to 4, well below 6.

[0211] (Example A) In the tables below, Examples are abbreviated as Ex and Comparative Examples are abbreviated as Comp Ex.

[0212] A formulation was prepared according to Table 1. All ingredients except TOLONATE™ HDT-90 were mixed. TOLONATE™ HDT-90 was then slowly added while stirring at 370-420 RPM using a propeller agitator. The resulting average particle size of Example 1 for the polyurea adduct was 40 μm, with a cumulative volume percentage of particles smaller than 10 μm of 10% and a cumulative volume percentage of particles larger than 20 μm of 82%. For Example 1, (PS at 90% by volume / PS at 10% by volume) = 4.9. [Table 1]

[0213] The paints were applied to glass, followed by measurements of tack-free time and Perso hardness. The paints were also applied to a black solvent-borne base coat that had been previously applied to an aluminum panel. The layer thickness of all samples was similar. The results are shown in Table 2. [Table 2]

[0214] The data in Table 2 clearly show that the use of polyurea particles according to the invention as a matting agent results in coatings of much higher quality. Compared to the formulation without a matting agent (Comparative Example 1), the coating containing polyurea particles according to the invention (Example 1) dries faster and has a shorter tack-free time, while the coating containing a silica matting agent unacceptably increases the tack-free time. Furthermore, the transparency of the coating containing the polyurea matting agent according to the invention is higher. This is evident from the lower haze value measured for Example 1 compared to Comparative Examples 2 and 3. Furthermore, it was particularly surprising that the gloss change after dry scratching and xenon resistance was much lower than the gloss change obtained using a silica-based matting agent.

[0215] (Example B) Film-forming resins containing polyurea matting agents were prepared according to Table 3 using the compositions listed under "Polyurea-Containing Polyols." The particle size was adjusted by process conditions. More specifically, the listed amount of benzylamine was predissolved in SETALUX® 1915 polyol in a reactor. Subsequently, TOLONATE™ HDT-90 (diluted to 50% solids with butyl acetate) was added to the reactor at 21-32°C while stirring at approximately 400 RPM (Ex 2 and 4 and Comp Ex 5) or 125 RPM (Ex 3 and Ex 5 and Comp Ex 4) using an anchor stirrer. Subsequently, crosslinkable compositions were prepared by adding the remaining ingredients listed under "Coatings" in Table 3. All samples were formulated equally at 58% solids by weight. [Table 3]

[0216] The paints were applied to a black solvent-borne basecoat that had been previously applied to aluminum panels. Haze and gloss were determined. The layer thickness of all samples was similar, ranging from 70 to 80 μm. The results are shown in Table 4. [Table 4]

[0217] From these data, it is clear that film-forming resins containing polyurea particles according to the present invention, in which the volume percentage of particles having a diameter of less than 10 μm is 40% or less and the volume percentage of particles having a diameter of more than 20 μm is 11% or more, exhibit a significant matting effect (Examples 2 to 5), whereas film-forming resins containing polyurea particles having a volume percentage of particles having a diameter of more than 10 μm or less than 11% of particles having a diameter of more than 20 μm, and therefore not according to the present invention (Comparative Examples 4 and 5), exhibit only a very slight, unacceptable matting effect compared to Comparative Example 1. Furthermore, Comparative Examples 4 and 5 exhibit very high haze.

[0218] (Example C) Film-forming resins containing polyurea matting agents and optional dispersants were prepared according to Table 5a. The listed amount of benzylamine was predissolved in SETALUX® 1915 polyol in a reactor, followed by charging TOLONATE™ HDT-90 (diluted to 60% solids with butyl acetate) to the reactor while stirring at approximately 125 RPM at 20-30°C using an anchor stirrer. The particle size distribution was then determined. The film-forming resins containing the polyurea adduct were diluted to 53% solids, followed by viscosity measurements. Furthermore, crosslinkable compositions were prepared by adding the ingredients shown in Table 5b. All samples were formulated equally at 55% crosslinkable composition solids. [Table 5a] [Table 5b]

[0219] The crosslinkable compositions according to Tables 5a and 5b were applied by drawing down onto a Leneta card in equal layer thicknesses. The haze and gloss were determined. The results are shown in Table 6. [Table 6]

[0220] The data in Tables 5a and 6 show that the addition of a dispersant to a film-forming resin containing polyurea particles according to the present invention also provided a good matting effect, resulting in low gloss values. Interestingly, the viscosity of the film-forming resin containing polyurea particles according to the present invention was significantly reduced by the addition of a dispersant, as evident when comparing Examples 7-9 with Example 6, or Examples 11 and 12 with Example 10, respectively. This reduction in viscosity is highly beneficial in achieving low VOCs when paints are formulated with the same viscosity. Furthermore, in spray applications, low viscosity is beneficial for achieving good leveling and appearance.

[0221] (Example D) A comparative example, Comp Ex 6, was prepared containing polyurea particles with a significantly lower (average) particle size than the inventive examples. Polyurea Resin 2 was prepared as follows: Resin 1 (described above) was charged to a 5-liter glass vessel equipped with a temperature jacket and agitator and heated to 30°C. Benzylamine was then added to the reaction vessel, and the mixture was homogenized for 10-15 minutes, followed by cooling in ice water. The agitator speed was increased to 750 rpm, and hexamethylene diisocyanate diluted with butyl acetate was added. The reaction mixture was stirred for 30 minutes and further diluted with butyl acetate to a solids content of 66.3 wt%. The resulting polyol component, Polyurea Resin 2, contained 4.6 wt% polyurea product and 61.7 wt% polyacrylate polyol. Table 7 shows the composition, as well as the polyurea particle size data and gloss of the final applied film. [Table 7]

[0222] Comp Ex 6 clearly shows that small polyurea particles having an (average) particle size outside the range described in this invention do not reduce the gloss of the crosslinkable composition.

[0223] (Example E) Compositions containing polyurea matting agents were prepared according to Table 8. For Examples 13 and 14, polyurea products were prepared in the RMA acceptor resin ACURE® 550-105 according to the following procedure. A mixture of the listed amounts of ACURE® 550-105, TOLONATE™ HDT-90, and DISPERBYK® 2150 was prepared in a stirred vessel. Subsequently, a solution of the listed amount of benzylamine in one-third of the listed amount of butyl acetate was pumped into the vessel with stirring, and processing conditions were adapted to achieve the targeted (average) particle size. More specifically, the solution was pumped into the vessel at a reaction temperature of 23-30°C while stirring at 400-450 RPM using an anchor-type stirrer. The particle size of the resulting polyurea-modified resin solution was determined according to the method described above, and the polyurea-containing solution was subsequently mixed with the remaining butyl acetate and the other ingredients listed in Table 8 to obtain the final real Michael addition (RMA) crosslinkable composition. In Example 15, both the RMA donor resin ACURE® 510-100 and the RMA acceptor resin ACURE® 550-105 were modified with a polyurea product according to the following procedure: 0.26 g of benzylamine and 0.04 g of DISPERBYK® 2150 were dissolved in 16.9 g of ACURE® 510-100. Subsequently, a separately prepared solution of 0.51 g of TOLONATE™ HDT-90 in 11.02 g of butyl acetate was added while stirring, and processing conditions were adjusted to obtain the targeted (average) particle size. More specifically, the separately prepared solutions were added at 23-30°C while stirring at 350-400 RPM using an anchor-type stirrer. The particle size of the resulting polyurea-modified RMA donor resin solution was determined. Separately, a mixture of 8.9 g of ACURE® 550-105, 0.04 g of DISPERBYK® 2150, and 0.63 g of TOLONATE™ HDT-90 was prepared, to which a solution of 0.32 g of benzylamine in 4.0 g of butyl acetate was added while stirring, and processing conditions were adapted to obtain the targeted (average) particle size.More specifically, the solution was added with stirring under processing conditions similar to those described above for Examples 13 and 14. The particle size of the resulting polyurea-modified RMA acceptor resin was determined. The polyurea-containing RMA donor and acceptor resin solutions were then mixed, and the remaining ingredients listed in Table 8 were added to obtain the final real Michael addition (RMA) crosslinkable composition of Example 15. [Table 8]

[0224] The paint was applied to a Leneta card by drawdown, and then gloss measurements were performed using a BYK gloss meter. The dry film thickness of all samples was similar, approximately 90 μm. Table 8 reveals that a polyurea loading of 3.0% relative to the solid binder (Ex 13) leads to a slight reduction in gloss compared to the reference clearcoat Comp Ex 7. The same is true for Ex 14, with a polyurea loading of 3.7% relative to the solid binder resin. At higher loadings (e.g., 6.5% in Ex 15), the polyurea particles provide very effective gloss reduction. Thus, while Examples 13 and 14 do show gloss reduction, the gloss reduction effect actually increases with increasing polyurea loading relative to the solid binder.

[0225] (Example F) Compositions containing polyurea and / or conventional silica-based matting agents and dispersants were prepared according to Table 9. In this case, to achieve the compositions listed under A in Table 9, a polyurea compound was prepared in an RMA donor resin according to the following procedure: A solution of ⅓ the listed amount of ACURE® 510-100 and the listed amount of DISPERBYK® 2150 in ⅓ the listed amount of butyl acetate was prepared in a stirred vessel. Subsequently, the following two separately prepared solutions were simultaneously pumped into the vessel: 1) the listed amount of 3-methoxypropylamine or benzylamine and ⅓ the listed amount of ACURE® 510-100 in ⅓ the listed amount of butyl acetate; 2) the listed amount of TOLONATE™ HDT-90 or DESMODUR® ultra 2822 and ⅓ the listed amount of ACURE® 510-100 in ⅓ the listed amount of butyl acetate. The processing conditions were adjusted to achieve the targeted particle size. More specifically, the two separately prepared solutions were simultaneously pumped into a vessel at 23-30°C while stirring at 350-400 RPM using an anchor-type agitator. The particle size distribution of the resulting polyurea-modified resin solution was determined, and the polyurea-containing solution was subsequently mixed with the pigment dispersant listed under B in Table 9 and the remaining ingredients listed under C in Table 9 to obtain the final real Michael addition (RMA) crosslinkable composition.

[0226] These compositions were applied to glass and metal panels by conventional spray application to a dry film thickness of approximately 70 μm, and the results are shown in Table 10. [Table 9-1] [Table 9-2]

[0227] Comp Ex 8 is a high-gloss white topcoat without any added matting additives. Clearly, the addition of ACEMATT® 3300 silica-based matting agent has a detrimental effect on the dry time of the RMA composition and the final hardness of the coating (Comp Ex 9, Table 10). Also, a somewhat higher amount of this additive is required to achieve sufficiently low gloss values ​​compared to Ex 17, which contains polyurea. [Table 10]

[0228] From Ex 16 it can be seen that significant matting is already achieved with 5.1% polyurea relative to the crosslinkable composition. By combining polyurea and silica matting agents the gloss can be reduced somewhat further (compare Ex 16 with Ex 18 and Ex 17 with Ex 19 respectively).

[0229] (Example G) The polyurea matte particles of the present invention were also combined with non-silica-based matting agents (Table 11). These compositions were prepared according to the general procedure described above. See also Example F. Ex 20 is a reference composition containing only polyurea particles. Comp Ex 10 and Comp Ex 11 contain only micronized thermosetting polymethylurea particles or wax-like micronized polymer particles, respectively. Ex 20 exhibits a strongly reduced gloss (Table 12), while Comp Ex 10 and Comp Ex 11 have significantly higher gloss. When the polyurea particles of the present invention are combined with DEUTERON® PMH-C (Ex 21) or CERAFLOUR® 1000 (Ex 22), gloss, especially at 60°, can be reduced compared to Ex 20, with only a slight drying delay and hardness loss (Table 12). [Table 11-1] [Table 11-2] [Table 12]

[0230] (Example H) Additional clear RMA crosslinkable compositions based on various malonate-functional polyester binders were prepared as shown in Table 13. Following the general procedure described above, in Examples 23 and 25, the polyurea component was prepared in ACURE® 550-105 RMA acceptor resin, and in Example 24, the polyurea component was prepared in ACURE® 510-100 donor resin. See also Example E. It is clear from the results shown in Table 13 that the effect of a certain loading of the polyurea particles of the present invention is powerful, with gloss reduction being similar regardless of the type of malonated polyester binder resin used (compare Ex 24 and Ex 25). It also shows that gloss can be reduced to very low levels by further increasing the loading of this particular polyurea adduct (compare Ex 23 and Ex 24). [Table 13]

[0231] (Example I) The film-forming, matte compositions of the present invention also show very good stability of the matte effect as a function of dry film thickness (DFT), as evidenced by Ex 26, Tables 14 and 15 (clear coatings) and Ex 27, Tables 14 and 16 (white pigmented coatings). This means that a strong and reproducible low gloss can be achieved regardless of the applied DFT. [Table 14] [Table 15] [Table 16]

[0232] (Example J) [Table 17] The crosslinkable compositions Comp Ex 12 and Comp Ex 13 contain polyurea particles based on diamines and diisocyanates, prepared according to the method described in JP 2629747. This method resulted in the formation of a high amount of polyurea particles with very large diameters, as represented by the relative particle size distribution width (Table 17). Furthermore, the average urea bond number of the polyurea compounds formed (by the method described in JP 2629747) was higher than six. Furthermore, the average particle size of the polyurea particles in Comp Ex 12 and Comp Ex 13 was similar to that of the polyurea particles according to the present invention, and gloss reduction was observed. Furthermore, more importantly, the resulting coatings suffered from severe clumping defects (leading to poor coating appearance), making the method described in JP 2629747 less suitable for preparing high-quality coatings with reduced gloss. Therefore, Comp Ex 12 and Comp Ex 13 cannot be used to prepare low-gloss coatings with good appearance.

[0233] (Example K) The crosslinkable compositions according to the present invention, comprising the particulate polyurea compounds according to the present invention, have been applied in UV-curable coating systems. In particular, by adjusting the urea composition, the content (of the polyurea compound) and the particle size (of the particles of the particulate polyurea compound), and by using appropriate additives to improve the viscosity and paint flow / appearance, it is possible to prepare (very) low gloss energy curable coatings, which can be effectively achieved when an acrylate-functional binder and / or crosslinker containing urea is present.

[0234] Particulate polyurea compounds according to the present invention were prepared as described above using trimethylolpropane trisacrylate (TMPTA) and ditrimethylolpropane tetraacrylate (DiTMPTA) as carrier resins. These resin compositions, listed under Section A in Table 18, were mixed with mixtures containing photoinitiators, listed under Section B in Table 18. Compositions containing particulate polyurea compounds, as well as comparative compositions without polyurea compounds and suitable properties, are listed in Table 18. These samples were bar-applied to metal, wood, and plastic substrates and cured by exposure to UV light after flash-off. Dry film thicknesses were approximately 40-50 μm. A Panacol-Elosol GmbH UV-H 254 UV lamp was used to cure the films. [Table 18-1] [Table 18-2]

[0235] The results for Ex 28 and Ex 29 in Table 18 clearly show that the gloss of TMPTA and DiTMPTA based UV cured coatings was very effectively reduced using the particulate polyurea compound according to the present invention compared to the corresponding references Comp Ex 14 and Comp Ex 15, which do not contain polyurea particles. Furthermore, Ex 30 reveals that the resin composition comprising the particulate polyurea compound can also be mixed with other resins to further adjust the degree of gloss reduction and other suitable coating properties.

[0236] (Example L) Crosslinkable compositions according to the invention comprising particulate polyurea compounds a2) according to the invention were also applied as low-solids clearcoat formulations for wood applications (Inventive Example 31 below) and compared with conventionally matte clearcoats comprising silica and wax-based matting agents and cellulose acetate butyrate (CAB) compounds to impart suitable rheological behavior to the coating (Comparative Example 16 below). The clearcoat compositions are shown in Table 19 and the test results are shown in Table 20.

[0237] To prepare resin composition A comprising particulate polyurea compounds a2) according to the invention, the amount of 3-methoxypropylamine listed in Table 19 was pre-dissolved in SETALUX® DA 450 polyol in a reactor, followed by dosing with DESMODUR® ultra 2822 at 20-30°C while stirring at about 125 RPM using an anchor stirrer. [Table 19] [Table 20]

[0238] As clearly shown in Table 20, Ex 31 provides significantly stronger matting performance than Comp Ex 16. When applied as a single layer of approximately 30 μm, Ex 31 exhibits low haze and very low gloss values, even at angles approaching horizontal (85°). Comp Ex 16 has higher haze, and gloss increases with increasing gloss measurement angle. When a second 30 μm layer is applied over the first layer, haze and gloss remain very low for Ex 31, but Comp Ex 16 exhibits a decrease in transparency (i.e., an increase in haze) and a significant reduction in the matting effect, especially at angles of 60° and 85°. It can be concluded that the results of Ex 31 according to the present invention are superior to those of Comp Ex 16. Indeed, Ex 31 clearly demonstrates that the absence of a CAB compound in a crosslinkable composition using the particulate urea compound of the present invention results in an improved matting effect (even at viewing angles approaching horizontal) and an improved stability of this effect depending on the number of layers applied.

Claims

1. Particulate polyurea compounds a2) for reducing the gloss of coatings, the volume percentage of particles of the particulate polyurea compound a2) having a diameter of less than 10 μm is not more than 40% and the volume percentage of particles of the polyurea product having a diameter of more than 20 μm is not less than 11%; the average particle size of the polyurea compound a2) is 11 to 80 μm; the polyurea compound a2) contains an average number of urea bonds per molecule of at least 2 and at most 6; Particulate polyurea compound a2).

2. The particulate polyurea compound a2) according to claim 1, wherein a relative particle size distribution width, which is the ratio of the particle size at 90% by volume of the particle size distribution to the particle size at 10% by volume of the particle size distribution, is 1 to 10.

3. 3) Particulate polyurea compound a2) according to claim 1 or 2, wherein the polyurea compound a2) has an average particle size of 15 to 80 μm.

4. Particulate polyurea compounds a2) according to any one of claims 1 to 3, wherein the polyurea compounds a2) are formed by reaction of polyisocyanates or their isocyanurate, biuret or uretdione derivatives or other derivatives of polyisocyanates with at least one amine.

5. the polyisocyanate is selected from the group consisting of hexamethylene-1,6-diisocyanate (HMDI), its isocyanurate trimer or biuret, trans-cyclohexylene-1,4-diisocyanate, para- and meta-xylylene diisocyanate, toluene diisocyanate, and mixtures thereof; and / or the amine is a monoamine and a primary amine; The particulate polyurea compound a2) according to claim 4.

6. The particulate polyurea compound a2) according to any one of claims 1 to 5, wherein the average number of urea bonds per molecule of the polyurea compound a2) is at least 2 and at most 4.

5.

7. Film-forming resins a1) including: at least two functional groups, each functional group having at least one type of functionality, and / or at least one functional group having at least two types of functionality, Particulate polyurea compounds a2) according to claims 1 to 6) optionally a dispersant a3), and optionally one or more compounds a4) different from compounds a1), a2) and a3); Resin composition A comprising:

8. 8. Resin composition A according to claim 7, wherein the particulate polyurea compound a2) is present in a content of 3 to 30% by weight, based on the total weight of the film-forming resin a1) and the particulate polyurea compound a2).

9. In light of the total weight of resin composition A, the particulate polyurea compound a2) is present in an amount of 2.5 to 20% by weight, the film-forming resin a1) is present in an amount of 1 to 97.5% by weight, dispersant a3) is present in an amount of 0 to 10% by weight, one or more compounds a4) are present in an amount of 0 to 96.5% by weight, The sum of the weight percentages does not exceed 100%. The resin composition A according to claim 7 or 8.

10. A resin composition A according to any one of claims 7 to 9, wherein the particulate polyurea compound a2) is prepared in the presence of the film-forming resin a1).

11. 11. Resin composition A according to any one of claims 7 to 10, wherein a dispersant a3) is present and is selected from the group consisting of polyesters, polyurethanes, and polyacrylates having pigment-affining anionic, cationic, or non-ionic groups, and high molecular weight block copolymers having basic pigment-affining groups, and combinations thereof.

12. The resin composition A according to any one of claims 7 to 11, wherein a4) is an organic solvent a4)-1 and / or an additive a4)-2.

13. a reactivity modifier e) selected from the group consisting of carboxylic acids, compounds of the general formula R1-SH, compounds containing an X-H group with a pKa<12, R2-OH, β-diketones, β-ketoesters, α-hydroxyketones, and mixtures thereof; R 1 is an alkyl, alkenyl, aryl or aralkyl group; X is C, N, P, O, or S; R 2 is an alkyl, alkenyl, aryl or aralkyl group; The resin composition A according to any one of claims 7 to 12.

14. the functional groups of the film-forming resin a1) are selected from the group consisting of hydroxy, primary amine, secondary amine, mercaptan, activated unsaturated C═C moieties, carboxylic acid, epoxide, isocyanate, activated methylene, methine species such as (derivatives of) acetylacetone, acetoacetate or malonate, and mixtures thereof; and / or the film-forming resin a1) is selected from the group consisting of polyester resins, (meth)acrylic resins, polycarbonate resins, polyether resins, polyurethane resins, amino resins, and mixtures and hybrids thereof; The resin composition A according to any one of claims 7 to 13.

15. A crosslinkable composition comprising the resin composition A according to any one of claims 7 to 14, film-forming resin b) and / or film-forming resin a1′), optionally a cross-linking agent c), optionally a catalyst d) for catalyzing the reaction of the functional groups of the film-forming resin a1) and / or the film-forming resin b) with the crosslinker c), if present, and / or with the film-forming resin b) and / or with the film-forming resin a1′); optionally a reactivity modifier e), optionally volatile organic compounds f), optionally a reactive diluent g), Optionally, another resin h), and Optionally, another matting composition i) different from or the same as the particulate polyurea compound a2). wherein the film-forming resins a1), a1′), and b), and the crosslinker c), if present, comprise at least two functional groups, each functional group having at least one type of functionality, and / or at least one functional group having at least two types of functionality; the film-forming resin a1) and / or the film-forming resin a1′) and / or the film-forming resin b) are capable of reacting with the film-forming resin b) and / or the film-forming resin a1′) and / or the crosslinker c), if present, The film-forming resin a1′) and the film-forming resin b) are different from or the same as the film-forming resin a1); Crosslinkable composition.

16. the functional groups of the film-forming resins a1′) and b) are selected from the group consisting of hydroxy, primary amine, secondary amine, mercaptan, activated unsaturated C═C moieties, carboxylic acid, epoxide, isocyanate, activated methylene, methine species such as (derivatives of) acetylacetone, acetoacetate or malonate, and mixtures thereof; and / or the film-forming resins a1′) and b) are selected from the group consisting of polyester resins, (meth)acrylic resins, polycarbonate resins, polyether resins, polyurethane resins, amino resins, and mixtures and hybrids thereof; The crosslinkable composition of claim 15.

17. 17. Crosslinkable composition according to claim 15 or 16, wherein the crosslinker c) comprises an oligomeric or polymeric compound having functional groups selected from the group consisting of isocyanate, hydroxy, primary amine, secondary amine, mercaptan, activated unsaturated C=C moiety, carboxylic acid, epoxide, activated methylene, methine species, such as (derivatives of) acetylacetone, acetoacetate or malonate, and mixtures thereof.

18. A crosslinkable composition according to any one of claims 15 to 17, wherein the amount of particulate polyurea compound a2) is 0.5 to 25% by weight based on the total amount of film-forming resin a1), particulate polyurea compound a2), and, if present, dispersant a3), non-volatile portion of additive a4)-2, crosslinker c), film-forming resin b), film-forming resin a1'), catalyst d), reactivity modifier e), reactive diluent g), resin h), and matting composition i) in the crosslinkable composition.

19. A method of coating an article or substrate to result in a reduced gloss coating having a gloss measurement of at most 45 gloss units at a 60° angle when applied at a dry film thickness (DFT) of 50-60 μm. (i) applying a crosslinkable composition according to claims 15 to 18, (ii) curing the applied composition A method comprising:

20. A substrate coated with the composition of any one of claims 15 to 18.

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