Release coatings

Abstract

The present invention relates to a composition comprising the following components: (I) at least one silicone (meth)acrylate (i) which laterally bears at least one (meth)acrylate group and in which the number of (meth)acrylate groups divided by the number of silicon atoms is on average 4.0% to 20.0%, (II) at least one (meth)acrylate (ii) which contains neither silicon atoms nor nitrogen atoms, (III) at least one amine (iii) which contains no silicon atoms, and optionally (IV) at least one compound (iv) selected from the group consisting of photoinitiators and photosensitisers, wherein the composition contains - 1 to 40 wt.%, preferably 5 to 35 wt.%, in particular 10 to 30 wt.% of component (I), - 5 to 90 wt.%, preferably 10 to 80 wt.%, in particular 21 to 75 wt.% of component (II), - 1 to 50 wt.%, preferably 2 to 45 wt.%, in particular 5 to 40 wt.% of component (III), and optionally - 0.1 to 15 wt.%, preferably 1 to 10 wt.%, in particular 1.5 to 9 wt.% of component (IV), where the figures in wt.% are in relation to the total composition. The invention further relates to the use of said composition as radiation-curing coating compounds, to a method for producing a release coating using said composition, and to the release coating obtainable by said method.

Description

202400147 Abroad 1 Release coatings The present invention relates to compositions that harden under atmospheric oxygen for the production of release coatings. Release coatings (often also referred to as adhesive coatings or release coatings) are well-known in the art. They are used, for example, in adhesive tapes or label laminates. Typically, a flat substrate, such as a plastic film, paper, or cardboard, is coated with a release coating. Compared to the uncoated substrate, the substrate with a release coating exhibits reduced adhesion to adhesive materials. These coatings often consist of silicones, as silicones offer excellent non-stick properties. Other applications include release films, protective films, and mold making, where a non-stick surface is required. Release coatings offer high resistance to adhesives and other adhesive substances. A release agent is a specific type of release coating. It is a special type of coating that also provides a non-stick surface, but is generally less robust than many other release coatings. Release agents are based on various chemical formulations, including silicones, resins, and other polymers, and may contain additives that enhance their non-stick properties. They are often more complex in their chemical composition and are primarily used in the printing and packaging industries, for example, on labels to prevent them from sticking together. A key characteristic of release agents is their typically low silicone content. Release agents provide a smooth, non-stick surface that is sufficient for their specific applications but less robust than many other release coatings.They tend to exhibit increased release properties or even to bond together. Release agents are often cured in an atmospheric environment. Two mechanisms are typically used to cure release coatings: In cationic curing, an epoxy-functional organosiloxane is polymerized using a photoinitiator that releases an acid upon irradiation. In radical curing, a silicone (meth)acrylate is polymerized using a photoinitiator that forms radicals upon irradiation. Radical polymerization of release coatings with a high silicone content is usually carried out under a protective atmosphere such as nitrogen. However, curing under atmospheric oxygen is desirable. Radical polymerization of release coatings with a low silicone content, such as release varnishes, is often carried out under atmospheric oxygen. The challenge here is that thin coatings cure poorly under atmospheric oxygen, especially at low radiation doses.The oxygen inhibition effect particularly affects surfaces that are oxygen-rich for extended periods. 202400147 Abroad 2 are exposed to various environments. The thinner the coating, the stronger the effect, as the high surface area to volume ratio promotes rapid oxygen diffusion. Silicone polymers and copolymers are frequently used for release coatings because they exhibit low surface energy and a low rotational barrier of the SiOSi bond. It is desirable for silicone-coated release papers and films to have a release force low enough to allow for easy removal, but not so low that they detach prematurely. Silicone polymers exhibit good oxygen solubility, and oxygen tends to diffuse much more rapidly in this medium than in pure organic polymers, which poses a challenge for curing under atmospheric conditions. W02000020517A2 describes the provision of a method for producing a coated substrate and a radiation-curable composition that enables a good curing rate in an air atmosphere. The radiation-curable composition comprises a compound with ethylene unsaturated bonds, an aliphatic maleimide compound, and an amine-functional acrylic polymer. The composition is intended to overcome oxygen inhibition effects, particularly in thin films. A disadvantage of such formulations is the significant toxicity of the maleimide compounds used. Furthermore, studies by JFGA Jansen (Surface Coatings International 2000 (10), pp. 502-507) show that the curing rate in thin films is slower than that achieved with conventional photoinitiators. US4831064A aims to provide improved radiation-curable compositions that cure rapidly in air when exposed to UV radiation. These compositions consist of a mixture of a mercaptoorganosilicone compound, a (meth)acrylamide-substituted organosilicone compound, and a radiation-activated photoinitiator. The presence of mercaptoorganosilicone compounds results in faster and / or more complete curing of the composition upon UV irradiation in the presence of air. A disadvantage of such formulations is the pungent odor typical of mercapto compounds. EP2192166A1 describes silicone-based release coatings that are cured in atmospheric oxygen. Specifically, EP2192166A1 refers to glossy coating compositions and their application methods, for example, for the production of self-adhesive labels. EP2192166A1 aims to overcome the disadvantages of conventional release coatings, which often have a matte surface and result in very high release values. The document describes compositions comprising a tetrafunctional acrylated monomer or oligomer, a silicone, and silica. These compositions can be cured with UV or electron beam radiation and do not require nitrogen for inerting. While such formulations yield acceptable release values, their disadvantage is... 202400147 Abroad 3, however, the insufficient hardening leads to an undesirable decrease in the adhesive strength of the adhesive when acting as a separating layer in contact with an adhesive. There was therefore still a need for radiation-curable compositions for the production of release coatings that can be cured under lye oxygen. The object of the present invention was therefore to provide precisely such compositions. These compositions should also enable suitable surface curing and / or through-curing, particularly when applied in thin layers. Release coatings produced from these compositions should also result in good residual adhesive strength after contact with the release coating. The release coatings should exhibit sufficient release properties. Surprisingly, it has now been found that compositions containing a special silicon (meth)acrylate in combination with a silicon-free (meth)acrylate and an amine solve this problem. A first object of the invention is therefore a composition containing the following components: (I) at least one silicone (meth)acrylate (i) which has at least one (meth)acrylate group laterally and in which the number of (meth)acrylate groups divided by the number of silicon atoms averages from 4.0% to 20.0%, (II) at least one (meth)acrylate (ii) containing neither silicon atoms nor nitrogen atoms, (III) at least one amine (iii) that does not contain silicon atoms, and optionally (IV) at least one compound (iv) selected from the group consisting of photoinitiators and photosensitizers, wherein the composition 1 to 40, preferably 5 to 35, in particular 10 to 30 wt.% of component (I), 5 to 90, preferably 10 to 80, in particular 21 to 75 wt.% of component (II), 1 to 50, preferably 2 to 45, in particular 5 to 40 wt.% of component (III), and optionally 0.1 to 15, preferably 1 to 10, in particular 1.5 to 9 wt.% of component (IV), wherein the wt.% values ​​refer to the entire composition. Another aspect of the invention is the use of the composition according to the invention as radiation-curing coating materials. 202400147 Abroad 4 Another object of the invention is a method for producing a release coating, comprising the following directly or indirectly successive steps: a. Applying the composition according to the invention to a surface; b. Curing the composition according to the invention by irradiation with UV radiation or electrons, preferably with UV radiation. Another object of the invention is a release coating obtainable by the inventive method. Advantageous embodiments of the invention are specified in the dependent claims, the examples, and the description. Furthermore, it is expressly pointed out that the disclosure relating to the subject matter of the present invention includes all combinations of individual features of the present and subsequent descriptions of the invention and the claims. In particular, embodiments of one subject matter according to the invention apply mutatis mutandis to embodiments of the other subject matter according to the invention. The objects according to the invention are described below by way of example, without the invention being limited to these exemplary embodiments. Where areas, general formulas, or classes of compounds are specified below, these are intended to include not only the corresponding areas or groups of compounds that are explicitly mentioned, but also all sub-areas and subgroups of compounds that can be obtained by removing individual values ​​(areas) or compounds. Where documents are cited within the scope of this description, their content is intended to be fully incorporated into the disclosure of the present invention. Unless otherwise stated, where average values ​​are given below, they are numerical means. If measured values, parameters or material properties are subsequently specified that are determined by measurement, then, unless otherwise stated, these are measured values, parameters or material properties measured at 25 °C and preferably at a pressure of 101325 Pa (standard pressure) and further preferably additionally at a relative humidity of 50%. All values ​​given in wt.% refer to the entire composition. The wt.% values ​​indicate the mass fraction of a specific component in the composition and therefore refer to the total mass of the composition. The term “(meth)acryl” stands for “methacryl” and / or “acryl”. 202400147 Abroad 5 As explained above, a first object of the invention is a composition comprising the following components: (I) at least one silicone (meth)acrylate (i) which has at least one (meth)acrylate group laterally and in which the number of (meth)acrylate groups divided by the number of silicon atoms averages from 4.0% to 20.0%, (II) at least one (meth)acrylate (ii) containing neither silicon atoms nor nitrogen atoms, (III) at least one amine (iii) that does not contain silicon atoms, and optionally (IV) at least one compound (iv) selected from the group consisting of photoinitiators and photosensitizers, wherein the composition 1 to 40, preferably 5 to 35, in particular 10 to 30 wt.% of component (I), 5 to 90, preferably 10 to 80, in particular 21 to 75 wt.% of component (II), 1 to 50, preferably 2 to 45, in particular 5 to 40 wt.% of component (III), and optionally 0.1 to 15, preferably 1 to 10, in particular 1.5 to 9 wt.% of component (IV), wherein the wt.% values ​​refer to the entire composition. It is particularly preferred that the composition 10 to 20 wt.% of component (I), 60 to 70 wt.% of component (II), 10 to 20 wt.% of component (III), and optionally contains 4 to 8 wt.% of component (IV), where the wt.% values ​​refer to the total composition. In a preferred embodiment, the composition consists of components (I), (II), (III) and optionally (IV). Even in this case, where the composition consists of components (I), (II), (III) and optionally (IV), the above values ​​in wt.% preferably apply. It is possible that the composition, comprising as component (I) at least one silicone (meth)acrylate (i) bearing at least one (meth)acrylate group laterally and in which the number of (meth)acrylate groups divided by the number of silicon atoms averages from 4.0% to 20.0%, additionally contains at least one further silicone (meth)acrylate that differs from silicone (meth)acrylate (i). In this case, it is preferred that the composition contains a maximum of 20 wt.%, preferably a maximum of 10 wt.%, and in particular 0 wt.% of further silicone (meth)acrylates that differ from silicone (meth)acrylates (i), wherein the wt.% values ​​refer to the entire composition. It is particularly preferred that the composition contains no other silicone (meth)acrylates besides silicone (meth)acrylates (i). 202400147 Abroad 6 further silicone(meth)acrylates. Since the composition contains 1 to 40, preferably 5 to 35, in particular 10 to 30 wt.% of component (I), it is correspondingly also preferred that the additional requirement applies that the composition contains 1 to 40, preferably 5 to 35, in particular 10 to 30 wt.% of silicone(meth)acrylates, wherein the values ​​in wt.% refer to the entire composition and also refer to the totality of silicone(meth)acrylates, i.e., the totality of silicone(meth)acrylates (i) and silicone(meth)acrylates that differ from silicone(meth)acrylates (i) together. It is therefore preferred that the composition 1 to 40, preferably 5 to 35, in particular 10 to 30 wt.% of component (I), 5 to 90, preferably 10 to 80, in particular 21 to 75 wt.% of component (II), 1 to 50, preferably 2 to 45, in particular 5 to 40 wt.% of component (III), and optionally 0.1 to 15, preferably 1 to 10, in particular 1.5 to 9 wt.% of component (IV), with the proviso that the composition contains 1 to 40, preferably 5 to 35, in particular 10 to 30 wt.% of silicone (meth)acrylates, wherein the wt.% values ​​refer to the entire composition. As described above, the composition comprises as component (I) at least one silicone (meth)acrylate (i) which carries at least one (meth)acrylate group laterally and in which the number of (meth)acrylate groups divided by the number of silicon atoms averages from 4.0% to 20.0%. The term "silicone (meth)acrylate" refers to silicone methacrylate and / or silicone acrylate. The term "(meth)acrylate group" refers to a methacrylic acid ester group and / or an acrylic acid ester group. The silicone (meth)acrylate (i) can therefore contain both methacrylic acid ester groups and acrylic acid ester groups, or only methacrylic acid ester groups, or only acrylic acid ester groups. Preferably, the (meth)acrylate groups are acrylic acid ester groups. Therefore, the silicone (meth)acrylate (i) is preferably a silicone acrylate (i). A silicone is generally understood to be a compound that has organic residues bonded to silicon atoms and structural units of the formula =Si-O-Si=, where "=" represents the three remaining valences of the silicon atom in question. Preferably, silicones are compounds composed of units selected from the group consisting of M = [RsSiOi / 2], D = [R2SiO2 / 2], T = [RSiOsc], and optionally additional units of the formula Q = [SiO4 / 2], where R represents a monovalent residue. The residues R can be chosen independently of one another and can be identical or different in pairwise comparisons. The residues R are organic residues, such as methyl groups, or inorganic residues, such as hydroxyl groups, although the number of organic residues in the silicone predominates.In connection with this invention, the designations M, D, T, and Q are used for organopolysiloxane building blocks. 202400147 Abroad 7 For reference to their significance, see W. Noll, Chemie und Technologie der Silicones, Verlag Chemie, Weinheim Bergstr., 1960, p. 2 ff. The silicone (meth)acrylate (i) carries at least one (meth)acrylate group laterally. This means that at least one (meth)acrylate group is not part of an M-unit. Such a laterally bound (meth)acrylate group is part of a D-unit and / or T-unit. Preferably, such a laterally bound (meth)acrylate group is exclusively part of a D-unit. It is preferred that the silicone (meth)acrylate (i) is a linear silicone (meth)acrylate (i). Such a linear silicone (meth)acrylate (i) consists only of D-units and M-units, specifically exactly two M-units and at least one D-unit. The less preferred branched silicone (meth)acrylates (i), on the other hand, additionally comprise T-units and / or Q-units. A value for the number of (meth)acrylate groups divided by the average number of silicon atoms of X% means that, on average, there are X (meth)acrylate groups for every 100 silicon atoms. The average value is to be understood as the numerical average across all molecules of the silicon (meth)acrylate (i) under consideration. It is preferred that for the silicon (meth)acrylate (i) the number of (meth)acrylate groups divided by the number of silicon atoms is on average 4% to 15%, preferably 4.5% to 10%, and in particular 5% to 8%. It is further preferred that the silicon(meth)acrylate (i) has on average 10 to 200, preferably 30 to 180, in particular 50 to 150 silicon atoms. It is also preferred that the silicone (meth)acrylate (i) has on average at least 2, preferably 2 to 10, in particular 3 to 8 (meth)acrylate groups. It prefers that the silicone(meth)acrylate (i) is selected from compounds of the general formula (I): M 1 mlM 2 m2D 1 dlD 2 d2 (I); with M 1 = [R 1 3SiOi / 2]; M 2 = [R 1 2R 2 SiOi / 2]; D 1 = [R 1 2SiO2 / 2]; D 2 = [R 1 R 2 SiO2 / 2]; wherein R 1 each independently selected from the group consisting of monovalent hydrocarbon residues, preferably with 1 to 12 carbon atoms; 202400147 Foreign country 8 preferably each independently selected is from the group consisting of having phenyl and methyl groups, in particular a methyl group; R 2each is independently selected from the group consisting of monovalent organic residues comprising carbon, hydrogen, and oxygen, preferably with 6 to 16 carbon atoms, which have 1 to 2 ester groups, wherein the ester groups are selected from the group consisting of (meth)acrylate groups and ester groups different therefrom, with the proviso that the compound of general formula (I) bears at least one (meth)acrylate group; wherein: d1 = 6 to 180, preferably 10 to 160, in particular 50 to 140; d2 = at least 2, preferably 2 to 10, in particular 3 to 8; m1 = 0 to 2, preferably 2; m2 = 0 to 2, preferably 0; with the proviso that: m1 + m2 = 2. The D units D 1 and D 2 They can be distributed arbitrarily in the polymer chain. Preferably, the residues R 2In compounds of general formula (I), the silicone (meth)acrylate (i) comprises monocarboxylic acid residue groups saturated with esters other than the (meth)acrylate groups, preferably selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, and benzoic acid ester groups, in particular acetic acid ester groups. More preferably, the saturated monocarboxylic acid ester groups are present in a numerical proportion of 0% to 20%, preferably greater than 0% to 15%, based on the total number of ester groups in the compounds of formula (I). It is preferred that the silicone (meth)acrylate (i) does not comprise any ester groups other than (meth)acrylate groups. It is therefore preferred that the silicone (meth)acrylate (i) comprises only (meth)acrylate groups and / or acrylate groups as ester groups. It is particularly preferred that the silicone (meth)acrylate (i) comprises only acrylate groups as ester groups. Preferably some or all of the remaining R 2selected from the group consisting of -CH2CH2CH2OCH2CH(OH)CH2OC(=O)CH=CH2, -CH2CH2CH2OCH2CH(OH)CH2OC(=O)C(CH3)=CH2, -CH2-CH2-CH2-O-CH2-C(CH2CH3)(CH2-OC(=O)-CH=CH2)2 and -CH2-CH2-CH2-O-CH2-C(CH2CH3)(CH2-OC(=O)-C(CH3)=CH2)2. Some or all of the remaining R are particularly preferred. 2 selected from the group consisting of -CH2CH2CH2OCH2CH(OH)CH2OC(=O)CH=CH2 202400147 Abroad 9 and -CH2-CH2-CH2-O-CH2-C(CH2CH3)(CH2-OC(=O)-CH=CH2)2. It is also preferred that for the compounds of general formula (I) the following additional requirements apply: the ratio of the sum (m2 + d2) to the sum (d1 + d2 + 2) is from 0.04 to 0.15, preferably from 0.045 to 0.1, in particular from 0.05 to 0.08; and / or the sum (d1 + d2 + 2) is equal to 10 to 200, preferably 30 to 180, in particular 50 to 150. The production of silicone(meth)acrylates (i) is known to those skilled in the art and is described, for example, in EP3168273A1 and EP0940422A1. Silicone (meth)acrylates can be produced, for example, by adding an allyl glycidyl ether or another suitable epoxide with an olefinic double bond to a hydrosilyl-functional silicone via a hydrosilylation reaction, and after addition, esterifying the epoxide with (meth)acrylic acid, thereby opening the epoxide ring. This process is described in DE3820294C1 and EP0979851 A1. Another method for producing silicone (meth)acrylates involves adding an alcohol with an olefinic double bond, for example, allyl alcohol, to a hydrosilyl-functional organosiloxane in the presence of a platinum catalyst, and then reacting the hydroxyl group of this alcohol with (meth)acrylic acid or a mixture of (meth)acrylic acid and optionally other, possibly saturated, monocarboxylic acids. This procedure is described, for example, in DE3810140C1 and EP0979851A1. As described above, the composition includes as component (II) at least one (meth)acrylate (ii) which contains neither silicon atoms nor nitrogen atoms. It is advantageous that the silicon-free (meth)acrylate (ii) consists of the elements carbon, hydrogen and oxygen, i.e. it contains no other atoms besides carbon, hydrogen and oxygen atoms. It is preferred that the (meth)acrylate (ii) has on average 1 to 8, preferably 2 to 7, and in particular 3 to 6 (meth)acrylate groups. The mean value is to be understood as the numerical average over all molecules of the (meth)acrylate (ii) under consideration. Suitable (meth)acrylates (ii) are described, for example, in European Coatings Tech Files, Patrick Glöckner et al. “Radiation Curing Coatings and printing inks”, 2008, Vincentz Network, Hannover, Germany. 202400147 Abroad 10 Suitable (meth)acrylates (ii) are also commercially available under the trade names Ebecryl TMPTA, Ebecryl OTA480, Ebecryl TPGDA, Ebecryl DPGDA, Ebecryl 892 and Ebecryl 1 1 from the company Allnex / Belgium. Suitable (meth)acrylates (ii) are also described in US2023287230A1, in particular in paragraph

[0099] . Geeignete (Meth)acrylate (ii) sind daher außerdem 1 ,3-Butylenglykol-Diacrylat, 1 ,4-Butandiol-Diacrylat, Neopentylglykol-Diacrylat, ethoxyliertes Neopentylglykol-Diacrylat, propoxyliertes Neopentylglykol-Diacrylat, 2-Methyl-1 ,3-propandiol-ethoxyacrylat, 2-Methyl-1 ,3- propandiol-Diacrylat, ethoxyliertes 2-Methyl-1 ,3-propandiol-Diacrylat, 3-Methyl-1 ,5-pentandiol- Diacrylat, 2-Buty l-2-ethy 1-1 ,3-propandiol-Diacrylat, 1 ,6-Hexandiol-Diacrylat, alkoxyliertes Hexandiol-Diacrylat, ethoxyliertes Hexandiol-Diacrylat, propoxyliertes Hexandiol-Diacrylat, 1 ,9- Nonandiol-Diacrylat, 1 ,10-Decandiol-Diacrylat, ethoxyliertes Hexandiol-Diacrylat, alkoxyliertes Hexandiol-Diacrylat, Diethylenglykol-Diacrylat, Triethylenglykol-Diacrylat, Tetraethylenglykol- Diacrylat, Polyethylenglykol-Diacrylat, propoxyliertes Ethylenglykol-Diacrylat, Dipropylenglykol- Diacrylat, Tripropylenglykol-Diacrylat, Polypropylenglykol-Diacrylat, Poly(tetramethylenglykol)- Diacrylat, Cyclohexandimethanol-Diacrylat,ethoxyliertes Cyclohexandimethanol-Diacrylat, alkoxyliertes Cyclohexandimethanol-Diacrylat, Polybutadien-Diacrylat, Hydroxypivalyl- Hydroxypivalat-Diacrylat, Tricyclodecandimethanol-Diacrylat, 1 ,4-Butandiylbis[oxy(2-hydroxy- 3,1-propandiol)]-Diacrylat, ethoxyliertes Bisphenol-A-Diacrylat, propoxyliertes Bisphenol-A- Diacrylat, propoxyliertes ethoxyliertes Bisphenol-A-Diacrylat, ethoxyliertes Bisphenol-F-Diacrylat, 2-(2-Vinyloxyethoxy)ethylacrylat, Dioxanglykol-Diacrylat, ethoxyliertes Glycerol-Triacrylat, Glycerol-Propoxylat-Triacrylat, Pentaerythritol-Triacrylat, Trimethylolpropan-Triacrylat, caprolactonmodifiziertes Trimethylolpropan-Triacrylat, ethoxyliertes Trimethylolpropan-Triacrylat, propoxyliertes Trimethylolpropan-Triacrylat, Tris(2-hydroxyethyl)isocyanurat-Triacrylat, e- Caprolacton-modifiziertes T ris(2-hydroxyethyl)isocyanurat-T riacry lat, Melaminacrylat-Oligomer, Pentaerythritol-Tetraacrylat, ethoxyliertes Pentaerythritol-Tetraacrylat, Di-Trimethylolpropan- Tetraacrylat,Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated dipentaerythritol hexaacrylate. The term "ethoxylated" refers to chain-extended compounds through the use of ethylene oxide, "propoxylated" refers to chain-extended compounds through the use of propylene oxide, and "alkoxylated" refers to chain-extended compounds using either ethylene oxide or propylene oxide, or both. Equivalent methacrylate compounds may also be used, although experts know that methacrylate compounds have lower reactivity than their equivalent acrylate counterparts. Preferably the (meth)acrylate (ii) is selected from the group consisting of trimethylolpropane triacrylate (TMPTA, CAS No.: 15625-89-5), tripropylene glycol triacrylate (TPGDA, CAS No.: 42978-66-5), dipropylene glycol triacrylate (DPGDA, CAS No.: 57472-68-1), dipentaerythritol hexaacrylate (DPHA, CAS No.: 29570-58-9) and propoxylated glycerol triacrylate (CAS No.: 52408-84-1). 202400147 Abroad 11 As described above, the composition includes as component (III) at least one amine (iii) that does not contain silicon atoms. The amine (iii) serves to ensure thorough curing of the composition, especially its surface. It is therefore often referred to as an amine synergist. It is preferred that the amine (iii) consists of the elements carbon, hydrogen, oxygen and nitrogen, i.e. it contains no other atoms except carbon, hydrogen, oxygen and nitrogen atoms. It is preferred that the amine (iii) has tertiary amino groups. It is particularly preferred that the amine (iii) has only tertiary amino groups. It is particularly preferred that the amine (iii) has no secondary or primary amino groups. It is also preferred that the amine (iii) has an amine number of 10 to 600, preferably 20 to 500, in particular 30 to 450 mg KOH / g, preferably determined according to DIN 53176:2002-11 . It is further preferred that the amine (iii) has (meth)acrylate groups. Preferably, the amine (iii) is therefore an amino(meth)acrylate. Suitable amino(meth)acrylates can be obtained by Michael addition of primary and / or secondary amino groups of corresponding amines to (meth)acrylate groups of (meth)acrylates, wherein the amines used to prepare the amino(meth)acrylates are employed in a stoichiometric under-reaction, such that some of the (meth)acrylate groups of the (meth)acrylates remain unreacted. The (meth)acrylates (ii) described above are particularly suitable as (meth)acrylates.Suitable amines for the production of amino(meth)acrylates include, for example, methylamine, ethylamine, isopropylamine, n-butylamine, hexylamine, neoheptylamine, 2-ethylhexylamine, decylamine, aniline, tolylamine, xylylamine, naphthylamine, benzylamine, phenethylamine, cyclopentylamine, methylcyclopentylamine, cyclohexylamine, dimethylcyclohexylamine, dimethylamine, dibutylamine, dioctylamine, N-methylamine, morpholine, piperazine, 2-methylpiperazine, N-methylpiperazine, N-propylpiperazine, piperidine, 2-ethylpiperidine, 4,4'-D-piperidyl, 1,3-di(4-piperidyl)propane, 1,5-di(4-piperidyl)pentane, ethylenediamine, diethylenetriamine, xylenediamine, and hexamethylenetetramine. ,2-diaminopropane, 1,3-diaminopropane, 3,3'-imino-bis-propylamine. Amino(meth)acrylates suitable as amines (iii) are disclosed, for example, in US3963771A, as are the (meth)acrylates and amines suitable for their preparation by Michael addition. 202400147 Abroad 12 It is preferred that the amine (iii) has on average 0.5 to 7.5, preferably 0.8 to 7.2, and in particular 1 to 5 (meth)acrylate groups. It is further preferred that the amine (iii) has on average 0.5 to 7.5, preferably 0.8 to 7.2, and in particular 1 to 5 tertiary amino groups. The mean values ​​are to be understood as the numerical average over all molecules of the amine (iii) under consideration. It is further preferred that the amine (iii) is selected from the group consisting of triethanolamine, Amietol M12 (methyldiethanolamine), Amietol M21 (dimethylethanolamine), acrylated amine compounds, amine-modified polyethers and amine-modified polyether acrylate oligomers. Suitable ami-no(meth)acry lates are commercially available from Sartomer and IGM, for example, under the designations CN341, CN3705, CN3715, CN3735, CN381, Photomer 4068, Photomer 4250, Photomer 4771, Photomer 4775, Photomer 4780, Photomer 4967, Photomer 5006. Suitable amines (iii) are also described, for example, in US2023287230A1, in particular in paragraph

[0082] Suitable amines (iii) are therefore also aromatic amines, such as 2-(dimethylamino)ethyl benzoate, N-phenylglycine, 4-(dimethylamino)benzoic acid, 1,1'-[(methylimino)di-2,1-ethanoldiyl] esters, and simple alkyl esters of 4-(N,N-dimethylamino)benzoic acid and other positional isomers of N,N-dimethylamino benzoic acid esters, wherein ethyl, amyl, 2-butoxyethyl and 2-ethylhexyl esters are particularly preferred, aliphatic amines, such as N-methyldiethanolamine, triethanolamine and triisopropanolamine, aminoacrylates and amine-modified polyether acrylates, such as EBECRYL 80, EBECRYL 81, EBECRYL 83, EBECRYL 85, EBECRYL 880, EBECRYL LEO 10551, EBECRYL LEO 10552, EBECRYL LEO 10553, EBECRYL 7100, EBECRYL P115, EBECRYL P116 and EBECRYL LED 03 available from ALLNEX, CN501, CN550, CN UVA421, CN3705, CN3715, CN3755, CN381 and CN386, all available from Sartomer, GENOMER 5142, GENOMER 5161, GENOMER 5271 and GENOMER 5275 from RAHN, PHOTOMER 4771, PHOTOMER 4967, PHOTOMER 5006, PHOTOMER 4775, PHOTOMER 5662,PHOTOMER 5850, PHOTOMER 5930 and PHOTOMER 4250, all available from IGM; LAROMER LR8996, LAROMER LR8869, LAROMER LR8889, LAROMER LR8997, LAROMER PO 83F, LAROMER PO 84F, LAROMER PO 94F, LAROMER PO 9067, LAROMER PO 9103, LAROMER PO 9106 and LAROMER P077F, all available from BASF; AGISYN 701, AGISYN 702, AGISYN 703, NeoRad P-81 and NeoRad P-85, all available from DSM-AGI. If UV radiation is used to cure the composition, the crosslinking / curing preferably takes place in the presence of photoinitiators and / or photosensitizers. As described above, the composition therefore optionally includes as component (II) at least one compound (iv) selected from the group consisting of photoinitiators and photosensitizers. 202400147 Abroad 13 It is preferred that the photoinitiator be selected from the group consisting of Norrish type I photoinitiators and Norrish type II photoinitiators. Examples include benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzil derivatives such as benzil and benzil dimethyl ketal (BDK), acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (TPO), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO-L), ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), α-hydroxyketones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, α-aminoketones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, thioxanthone derivatives such as 2-isopropylthioxanthone (ITX), 2,4-diethylthioxanthone (DETX), aryl ketones such as benzophenone, 2-ethylhexyl 2-([1,T-biphenyl]-4-ylcarbonyl) benzoate, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, 4-methyl benzophenone, Michler's ketone, Oxime esters such as 1-[4-(phenylthio)phenyl]ethanone O-[(2-ethylhexyl)oxy]oxime, polymeric photoinitiators such as polymeric benzoin ether, polymeric benzil ketal,Polymeric benzophenone, polymeric acylphosphine oxide, and others such as camphorquinone (CQ) and anthraquinone derivatives. Other common photoinitiators are described, for example, in "A Compilation of Photoinitiators Commercially Available for UV Today" (K. Dietliker, SITA Technology Ltd, London 2002). The photoinitiators and / or photosensitizers are preferably soluble in the compositions according to the invention, more preferably soluble in a mass fraction of 0.1% to 15%, in particular 1% to 10%, based on the mass of the total composition. A preferred composition contains, in addition to components (I), (II) and (III) and the optional component (IV), one or more additional components that differ from components (I), (II), (III) and (IV). A preferred composition contains, in addition to components (I), (II) and (III) and the optional component (IV), one or more additional components selected from the group consisting of fillers, pigments, solvents, curing accelerators, anti-misting additives, stabilizers such as phosphites or hindered amine light stabilizers (HALS), antioxidants and oxygen scavengers. It is further preferred that the composition according to the invention is used as a radiation-curing coating compound. Preferably, the composition according to the invention is a radiation-curing coating compound. The composition according to the invention is preferably used as a UV-curable coating compound for the production of release coatings, in particular release lacquers. 202400147 Abroad 14 It is therefore preferred that the composition according to the invention can be cured by irradiation with UV radiation or electrons, preferably with UV radiation. Furthermore, it is preferred that the composition according to the invention is used in such a way that the cured coating mass is a release coating. Another object of the invention is accordingly the use of the composition according to the invention as a radiation-curing coating compound. It is preferred that the radiation-curing coating compound is a release agent composition. A release agent composition is a composition that, when applied over a surface and cured, forms a release agent. The radiation-curing coating mass according to the invention can be cross-linked three-dimensionally by free radicals and cures thermally within a very short time to a mechanically and chemically resistant layer with the addition of, for example, peroxides or under the influence of high-energy radiation, such as UV or electron radiation, which, with a suitable composition of the coating mass according to the invention, has predeterminable adhesive properties as well as adhesion properties. Another object of the invention is a method for producing a release coating, comprising the following directly or indirectly successive steps: a. Applying the composition according to the invention to a surface; b. Curing the composition according to the invention by irradiation with UV radiation or electrons, preferably with UV radiation. In the production of the release coating, it is preferred that the surface be the surface of a substrate, preferably a sheet substrate. The composition according to the invention can be applied to one or both sides of the sheet substrate. Preferably, the sheet substrate is selected from the group consisting of paper, fabric, metal foils, and plastic films. The substrate can be smooth or provided with surface structures. Polypropylene and polyethylene films are particularly preferred substrates. Suitable UV radiation sources for curing the coating compositions according to the invention are medium-pressure mercury vapor lamps, optionally doped, or low-pressure mercury vapor lamps, UV LED lamps, or so-called excimer lamps. The UV lamps can be polychromatic or monochromatic. Preferably, the emission range of the lamp lies within the absorption range of the photoinitiators and / or photosensitizers. 202400147 Abroad 15 The composition according to the invention can be cured in an air atmosphere as well as in an atmosphere flooded with inert gas. In an atmosphere flooded with inert gas, the oxygen content can be between 10 and 10,000 ppm. Use in an air atmosphere is preferred. Another object of the invention is a release coating obtainable by the inventive method. The release coating according to the invention is used, for example, in adhesive tapes, labels, packaging for self-adhesive hygiene products, food packaging, self-adhesive thermal papers, or cover sheets for bitumen roofing membranes. The release coating exhibits good release properties against the adhesive materials used in these applications. The release effect against adhesive materials, in technical applications mostly adhesive tapes or labels, is expressed by the release value, with a lower release value indicating good release. The release value is determined according to FINAT Handbook 10th Edition, The Hague / NL, 2020, under the designation FTM 10, with the modification that storage is carried out under pressure at 40 °C. The release value depends on the quality of the release coating (e.g., uniformity, thickness, and / or smoothness of the coating), the adhesive material or adhesive, and the test conditions. Therefore, identical adhesives or adhesive materials and test conditions should be used to evaluate release coatings. The adhesive tape tesa® 7475, trademark of Tesa SE, Germany, Hamburg, in a width of 2.5 cm, is used to determine the release values. Preferably, the release coatings according to the invention have release values ​​of a maximum of 250 cN / 2.5 cm, preferably of a maximum of 220 cN / 2.5 cm, in particular of a maximum of 200 cN / 2.5 cm. Preferably, the separating coatings according to the invention have separation values ​​of at least 10 cN / 2.5 cm, preferably at least 20 cN / 2.5 cm, in particular at least 25 cN / 2.5 cm. Preferably, the release coatings according to the invention have release values ​​of 10 to 250 cN / 2.5 cm, preferably of 20 to 220 cN / 2.5 cm, in particular of 25 to 200 cN / 2.5 cm. The release coating also exhibits good short-term residual tack (Quick Subsequent Adhesion, QSA). Short-term residual tack is a measure of the cross-linking of the 202400147 Abroad 16 Silicone components of the release coating. If non-polymerized and therefore migratory silicone components are present, increasingly lower values ​​for quick subsequent adhesion are achieved with an increasing proportion of such components. Values ​​above 65% are considered acceptable. The quick subsequent adhesion (QSA) is determined according to the test method from the FINAT Handbook, 10th edition, The Hague / NL, 2020, designated FTM 11, with the difference that the test tape is stored in contact with the release coating for one minute and the standard surface is an untreated BOPP surface. The adhesive tape used is tesa® 7475 (Tesa SE, Germany, Hamburg). Preferably, the release coatings according to the invention have a quick subsequent adhesion (QSA) of at least 65%, preferably at least 75%, and particularly at least 85%, with 100% being the maximum achievable value. The present invention is described with reference to the following examples, without the invention, the scope of which is evident from the entire description and the claims, being limited to the embodiments mentioned in the examples. 202400147 Abroad 17 Examples General methods: The silicone acrylates were characterized using the 1 Dog 29 Si NMR spectroscopy. The 1 In accordance with this invention, H-NMR samples were dissolved in CDCH and treated against tetramethylsilane (TMS) as an external standard at a measurement frequency of 400 MHz in a Bruker 400 spectrometer equipped with a BBI probe head at 22°C [8( 1 H) = 0.0 ppm] measured. The 29Si-NMR samples were measured at a measurement frequency of 79.49 MHz in a Bruker Avance III spectrometer equipped with a 287430 probe head with a 10 mm slit width at 22°C dissolved in CDCH and against tetramethylsilane (TMS) as an external standard [8( 29 Si) = 0.0 ppm] measured. Synthesis of silicone acrylates (Component I): Silicone acrylates S1 to S7 were prepared according to the synthesis procedure from EP3168273A1. Silicone acrylate S8 was prepared according to the synthesis procedure from EP0940422A1. The characterization of silicone acrylates S1 to S8 is given in Table 1. 02400147 Abroad 18 Table 1: Silicone acrylates according to formula (I) a] : according to the invention b] : not according to the invention c] : X% = X acrylate groups per 100 Si atoms d] : -CH2-CH2-CH2-O-CH2-CH(OH)-CH2-OC(=O)-CH=CH2e] : -CH2-CH2-CH2-O-CH2-C(CH2CH3)(CH2-OC(=O)-CH=CH2)2 202400147 Abroad 19 Raw materials used Trimethylolpropane triacrylate (TMPTA), organic triacrylate monomer, Allnex, Belgium Dipentaerythritol hexaacrylate (DPHA), organic hexa / pentaacrylate monomer, Allnex, Belgium OTA 480, propoxylated glyceryl triacrylate, Allnex, Belgium Photomer 4967, acrylated amine adduct, IGM Resins, China Omnirad 991, benzophenone derivative, IGM Resins, China. Production of the release coating compositions: The release coating compositions F1 to F14 were produced by mixing the components according to Table 2. 202400147 Abroad 20 Table 2: Release coating compositions. Values ​​in weight percent based on the total mass of the release coating formulation. 202400147 Abroad 21 a] : according to the invention [b] : not according to the invention Application-related review Production of the release coatings: To produce the release agent compositions (hereinafter also referred to simply as "formulations"), the components were mixed according to Table 2 and stirred by hand with a spatula until no inhomogeneity was visible. The release agent compositions thus produced were applied to a flat substrate. In all examples, this was a 15 cm wide BOPP film (BOPP: biaxially oriented polypropylene), which had previously undergone corona treatment with a generator output of 1 kW. The release agent compositions were coated using a 5-roll coating machine from Maan (Maan Group, 8102 HR Raalte, Netherlands) at a weight of approximately 1 g / m². 2applied and cured by irradiation with UV light from a medium-pressure mercury vapor lamp by IST® Metz GmbH (Nürtingen, Germany) at 160 W / cm² under air atmosphere and a web speed of 20 m / min. The separation value and the short-term residual adhesion (QSA) were then tested on the coated samples. Separation value: The release effect against adhesive substances, usually in the form of adhesive tapes or labels, is expressed by the release value, with a lower release value indicating a good release effect. The release value depends on the quality of the release coating, the adhesive itself, and the test conditions. Therefore, the same adhesives and test conditions should be used to evaluate release coatings. To determine the release values, adhesive tapes were cut to a width of 2.5 cm and their adhesive side was applied to the release coating under test. This test was carried out according to FINAT Handbook 10th Edition, The Hague / NL, 2020, under the designation FTM 10, with the modification that storage was performed under pressure at 40 °C. The adhesive tape used was tesa® 7475. 202400147 Abroad 22 (Trademark of Tesa SE, Germany, Hamburg). The values ​​given are the average of two measurements and are expressed in the unit [cN / 2.5 cm]. Quick Subsequent Adhesion (QSA): The short-term residual tack (QSA) was determined according to the test procedure from the FINAT Handbook, 10th edition, The Hague / NL, 2020, under the designation FTM 11, with the difference that the test tape was stored in contact with the release liner for one minute and the standard surface was an untreated BOPP surface. The tape used was tesa® 7475 (Tesa SE, Germany, Hamburg). The short-term residual tack is a This measure indicates the crosslinking of the silicone components in the release coating. If non-polymerized and therefore migratory silicone components are present, progressively lower values ​​for rapid subsequent adhesion are achieved with an increasing proportion of such components. Values ​​above 65% are considered acceptable. The results for release values ​​and short-term residual tack (QSA) are shown in Table 1. 202400147 Abroad 23 Results'. The results of the application-related testing are summarized in Table 3. Table 3: Results of the application-related testing (separation value in cN / 2.5 cm according to Storage for 24 hours at 40 °C; short-term residual tack (QSA) in %). a] : according to the invention [b] : not according to the invention [c] : Composition did not harden Table 3 shows that the formulations F1, F2, F3, F9, F10, F11 and F19 according to the invention achieve separation values ​​of 45 to 170 cN / 2.5 cm with simultaneous QSA values ​​of at least 65% 202400147 Abroad 24 exhibit. Particularly noteworthy is the crosslinking with a coating weight of 1 g / m². 2 The test was performed under atmospheric air, resulting in exceptionally good QSA. Simultaneously, a separation value in the range of below 200 cN / 2.5 cm can be achieved, which is suitable for many applications. In contrast, the non-inventive formulations F4, F12, and F18, with QSA values ​​exceeding 80%, also exhibit very good crosslinking; however, their release values ​​exceeding 400 cN / 2.5 cm are too high for many applications. Conversely, the non-inventive formulations F5 to F8, F13 to F16, and F20 to F22 show that while low release values ​​of 16 to 60 cN / 2.5 cm are achieved, their QSA values ​​are less than 66%, i.e., very low. Such release coatings strongly influence the adhesive and its bond strength, severely limiting their application. Without component (II) or (III), the formulations cannot be cured or result in very high release values ​​(see F17 and F18).

Claims

202400147 Abroad 25 Patent claims 1. Composition containing the following components: (I) at least one silicone (meth)acrylate (i) which has at least one (meth)acrylate group laterally and in which the number of (meth)acrylate groups divided by the number of silicon atoms averages from 4.0% to 20.0%, (II) at least one (meth)acrylate (ii) containing neither silicon atoms nor nitrogen atoms, (III) at least one amine (iii) that does not contain silicon atoms, and optionally (IV) at least one compound (iv) selected from the group consisting of photoinitiators and photosensitizers, wherein the composition 1 to 40, preferably 5 to 35, in particular 10 to 30 wt.% of component (I), 5 to 90, preferably 10 to 80, in particular 21 to 75 wt.% of component (II), 1 to 50, preferably 2 to 45, in particular 5 to 40 wt.% of component (III), and optionally 0.1 to 15, preferably 1 to 10, in particular 1.5 to 9 wt.% of component (IV), wherein the wt.% values ​​refer to the total composition.

2. Composition according to claim 1, characterized in that the composition contains 1 to 40, preferably 5 to 35, in particular 10 to 30 wt.% of silicone (meth)acrylates.

3. Composition according to claim 1 or 2, characterized in that for the silicone (meth)acrylate (i) the number of (meth)acrylate groups divided by the number of silicon atoms is on average 4% to 15%, preferably 4.5% to 10%, in particular 5% to 8%.

4. Composition according to one of claims 1 to 3, characterized in that the silicon(meth)acrylate (i) has on average 10 to 200, preferably 30 to 180, in particular 50 to 150 silicon atoms.

5. Composition according to one of claims 1 to 4, characterized in that the silicone (meth)acrylate (i) has on average at least 2, preferably 2 to 10, in particular 3 to 8 (meth)acrylate groups. 202400147 Abroad 26 6. Composition according to any one of claims 1 to 5, characterized in that the silicone (meth)acrylate (i) is selected from compounds of the general formula (I): M 1 mi M 2 m2D 1 di D 2 d2 (I); with M 1 = [R 1 3SiOi / 2]; M 2 = [R 1 2R 2 SiOi / 2]; D 1 = [R 1 2SiO2 / 2]; D 2 = [R 1 R 2 SiO2 / 2]; wherein R 1each independently selected is from the group consisting of monovalent hydrocarbon residues, preferably with 1 to 12 carbon atoms; preferably each independently selected is from the group consisting of with phenyl and methyl groups, in particular a methyl group; R 2each is independently selected from the group consisting of monovalent organic residues comprising carbon, hydrogen, and oxygen, preferably with 6 to 16 carbon atoms, which have 1 to 2 ester groups, wherein the ester groups are selected from the group consisting of (meth)acrylate groups and ester groups different therefrom, with the proviso that the compound of general formula (I) bears at least one (meth)acrylate group; wherein: d1 = 6 to 180, preferably 10 to 160, in particular 50 to 140; d2 = at least 2, preferably 2 to 10, in particular 3 to 8; m1 = 0 to 2, preferably 2; m2 = 0 to 2, preferably 0; with the proviso that: m1 + m2 = 2.

7. Composition according to any one of claims 1 to 6, characterized in that the (meth)acrylate (ii) has on average 1 to 8, preferably 2 to 7, in particular 3 to 6 (meth)acrylate groups.

8. Composition according to any one of claims 1 to 7, characterized in that the amine (iii) has tertiary amino groups. 202400147 Abroad 27 9. Composition according to any one of claims 1 to 8, characterized in that the photoinitiator is selected from the group consisting of Norrish type I photoinitiators and Norrish type II photoinitiators.

10. Composition according to one of claims 1 to 9, characterized in that it can be cured by irradiation with UV radiation or electrons, preferably with UV radiation.

11. Use of the composition according to any one of claims 1 to 10 as a radiation-curing coating compound.

12. Use according to claim 11, characterized in that the radiation-curing coating compound is a release coating composition.

13. Method for producing a release coating, comprising the following directly or indirectly successive steps: a. Applying the composition according to any one of claims 1 to 10 to a surface; b. Curing the composition by irradiation with UV radiation or electrons, preferably with UV radiation.

14. Release coating obtainable by the method of claim 13.

Images