Silicone urethane (meth)acrylate and their use in coating compositions

Abstract

The present invention relates to a composition containing a silicone urethane (meth)acrylate having at least three (meth)acrylate groups and no more urethane groups than (meth)acrylate groups, a method for preparing the composition, and a release coating, a protective film, and a protective coating that can be obtained by curing the composition.

Description

Technical Field

[0001] The present invention relates to a composition containing a silicone urethane (meth)acrylate having at least three (meth)acrylate groups and no more urethane groups than (meth)acrylate groups, a method for preparing the composition, and a release coating, a protective film, and a protective coating that can be obtained by curing the composition.

[0002] The use of silicone urethane (meth)acrylate as a constituent of compositions such as 3D printing resins and coating compositions is known in the prior art.

[0003] Korean Patent Application Publication No. 20170128955 discloses a silicone urethane (meth)acrylate as a photocurable polymer for 3D printing. In Example 1, the silicone urethane acrylate is prepared by reacting 1 mole of hydroxy-terminated polydimethylsiloxane with 2 moles of hexamethylene diisocyanate (HDI), followed by 2 moles of hydroxyethyl acrylate (HEA). In Example 2, the silicone urethane acrylate is prepared in the same manner using isophorone diisocyanate (IPDI) instead of HDI. The silicone urethane acrylates of these Examples 1 and 2 have two acrylate groups and four urethane groups. In Example 3, the silicone urethane methacrylate is prepared by reacting 1 mole of hydroxy-terminated polydimethylsiloxane with 2 moles of 2-isocyanatoethyl methacrylate, which is a dangerous and toxic compound. The polymer of Example 3 has two methacrylate groups and two urethane groups. It is further described that these photocurable polymers are flexible, have a high photocuring rate, and are easy to process.

[0004] Chinese Patent Application Publication No. 106519182 discloses a silicone urethane acrylate for use in the field of release coatings. The silicone urethane acrylate is prepared by a method including the following steps. (1) A step of reacting an organosilicon glycol and a diisocyanate in a ratio such that the molar ratio of the hydroxyl group to the isocyanato group is 1:2. (2) A step of reacting hydroxyethyl acrylate or hydroxyethyl methacrylate with the prepolymer obtained in step (1) in a ratio such that the molar ratio of the hydroxyl group to the isocyanato group is 1:1.

[0005] The organosilicon glycol is a chain-type silicon glycol having an organic group containing two hydroxyl groups at one of the chain ends. The diisocyanate is preferably selected from toluene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate. The obtained silicone urethane acrylate has two (meth)acrylate groups and four urethane groups.

[0006] Chinese Patent Application Publication No. 109577077 discloses a method for preparing a self-adhesive release paper by electron beam curing. The release paper includes a base paper layer and a release coating, and the latter is obtained by electron beam curing of a release coating composition containing 50 to 100 parts of a silicone-modified urethane acrylate, 0 to 50 parts of a silicone-modified polyacrylate, and 10 to 20 parts of a reactive diluent.

[0007] However, silicone urethane (meth) acrylates known in the art as components of coating compositions typically exhibit only moderate photocuring rates, are highly viscous at room temperature, or are even solids, which makes processing difficult. To improve their processability, the processing of silicone urethane (meth) acrylates is carried out at higher temperatures or larger amounts of solvents or reactive diluents are added, which can result in other drawbacks such as increased energy consumption, additional process steps for removing the solvents, and / or possible adverse effects on the desired properties of the cured product. Also, a fast curing rate and an increased curing depth are preferred to facilitate processing. Furthermore, the cured product preferably is flexible and has good mechanical properties such as a high elongation at break. It is also preferred that the cured product is an elastomeric material, i.e., the product should return to its original shape after deformation such as elongation. The surface of the cured product should be smooth and have good release properties. The surface of the cured product should also have good scratch resistance. In the synthesis of silicone urethane (meth) acrylates, it is also necessary to avoid very highly toxic or very dangerous compounds.

[0008] Accordingly, there is still a need to provide silicone urethane (meth) acrylates having advantages over the prior art as components of coating compositions and compositions containing said silicone urethane (meth) acrylates. Thus, the problem addressed by the present invention was to overcome at least one drawback of the prior art.

[0009] Surprisingly, it has been found that the subject matter of the independent claims overcomes at least one drawback of the prior art.

[0010] Accordingly, the object of the present invention is achieved by the subject matter of the independent claims. Preferred embodiments of the present invention are specified in the dependent claims, the examples, and the description.

[0011] According to a first aspect of the present invention, the following components: (a) At least one silicone urethane (meth)acrylate having the following: - At least three (meth)acrylate groups, and - A urethane group not more than the (meth)acrylate group, preferably the same number of urethane groups as the (meth)acrylate group; (b) At least one organic (meth)acrylate having no silicon atom; (c) At least one silicone (meth)acrylate having no urethane group; (d) Optionally, at least one curing catalyst; (e) Optionally, at least one additive; (f) Optionally, at least one solvent; A composition comprising or consisting of: - 20 to 70%, preferably 25 to 60%, more preferably 25 to 50% (by weight) of component (a); - 20 to 80%, preferably 30 to 70%, more preferably 40 to 65% (by weight) of component (b); - At least 1 to 60%, preferably 2 to 40%, more preferably 5 to 25% (by weight) of component (c); - 0 to 5%, preferably 0.1 to 3%, more preferably 0.5 to 2.5% (by weight) of component (d); - 0 to 20%, preferably 0 to 10%, more preferably 0 to 5% (by weight) of component (e); - 0 to 10%, preferably 0 to 5%, more preferably 0 to 1% (by weight) of component (f); wherein it is preferably contained based on the total weight of components (a) to (f) and / or based on the total weight of the composition, and more preferably based on the total weight of the composition. A composition is provided, which is characterized by the above.

[0012] According to a second aspect of the present invention, the following steps: (i) A step of preparing a mixture of component (a) and component (f); (ii) preparing the mixture by adding at least one of components (b) to (e), preferably component (b) and / or (c), to the mixture of step (i); (iii) (essentially) removing component (f) from the mixture of step (ii); (iv) optionally, if said component has not been added in step (ii), preparing the mixture by adding at least one of components (b) to (e) to the mixture of step (iii), A method for preparing said composition is provided, which comprises or consists of the above.

[0013] According to a third aspect of the present invention, preferably the following indirectly or directly consecutive steps: a. applying said composition to a surface; b. curing said composition, preferably by irradiating with UV radiation A method for preparing a release coating, protective film, or protective coating is provided, which comprises the above.

[0014] According to a fourth aspect of the present invention, there is provided a release coating, protective film, or protective coating which can be obtained by curing said composition, preferably by said method.

[0015] As used herein, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise.

[0016] The terms "comprising" and "comprises" as used herein are synonymous with "including", "includes", "containing" or "contains", are inclusive or open-ended, and do not exclude additional unrecited members, elements, or method steps.

[0017] It should be understood that when quantities, concentrations, dimensions, and other parameters are expressed in the form of a range, a desired range, an upper limit value, a lower limit value, or a desired upper limit value and a limit value, any range that can be obtained by combining any upper limit value or desired value with any lower limit value or desired value is also specifically disclosed, regardless of whether the resulting range is explicitly referred to in the context.

[0018] The following reports a numerical range in the form of "X to Y". When X and Y represent the limits of the numerical range, this is synonymous with the description "at least X to Y or less" unless otherwise specified. Therefore, the description of the range includes the range limits X and Y unless otherwise specified.

[0019] The terms "preferred" and "preferably" are frequently used in this specification to refer to embodiments of the present disclosure that can provide specific benefits under specific circumstances. However, the listing of one or more desired or preferred embodiments does not mean that other embodiments are not useful, nor is it intended to exclude those other embodiments from the scope of the present disclosure.

[0020] When measured values, parameters, or material properties determined by measurement are reported below, unless otherwise specified, these are measured values, parameters, or material properties measured at a pressure of 25°C and preferably 101,325 Pa (standard pressure).

[0021] As used in this specification, room temperature (RT) is 23°C ± 2°C.

[0022] The expression "(meth)acryl" represents "methacryl" and / or "acryl". Therefore, the expression "(meth)acrylate" represents "methacrylate" and / or "acrylate". As used in this specification, "acrylate" refers to "acrylate ester", and "methacrylate" refers to "methacrylate ester".

[0023] In the context of the present invention, silicone urethane (meth)acrylate is understood to mean an organosiloxane containing urethane groups and having methacrylate groups and / or acrylate groups, hereinafter also referred to as (meth)acrylate groups. Organosiloxanes are hereinafter also simply referred to as siloxanes.

[0024] Organosiloxane is understood to mean a compound having silicon atoms and organic radicals bonded to the structural unit of the formula ≡Si-O-Si≡, where "≡" represents the remaining three valences of the silicon atom in question. Organosiloxanes preferably have the formula M = [R3SiO 1 / 2 , D = [R2SiO 2 / 2 , T = [RSiO 3 / 2 and are composed of units selected from the group consisting of, and optionally also have units of the formula Q = [SiO 4 / 2 (where R is a monovalent organic radical). The radicals R may each be independently selected here and may be the same or different when compared in pairs. The group R can also be partially replaced by non-organic monovalent radicals such as, for example, hydroxyl groups or chlorine. Reference is made here by way of reference to the M, D, T, Q nomenclature used herein to describe the structural units of organosiloxanes, which is W. Noll, Chemie und Technologie der Silicone [Chemistry and Technology of the Silicones], Verlag Chemie GmbH, Weinheim (1960), page 2 ff.

[0025] The various repeating units in the following formulas (C), (F), (Q) and (S) can be statistical distributions. The statistical distributions may have a blockwise structure with any number of blocks and any arrangement, or may be subject to a randomized distribution. They may also have an alternating structure, or may form a gradient along the chain if a chain is present. In particular, they can also form any mixed form in which groups of different distributions can optionally follow one another. Specific embodiments can be defined below in that features such as indices or structural components or ranges or statistical distributions are subject to limitations according to the embodiment. All other features not affected by the limitations remain unchanged.

[0026] If the molecule / molecular fragment has one or more stereocenters (asymmetric centers), or can be distinguished into isomers due to symmetry, or can be distinguished into isomers due to other effects, such as restricted rotation, all possible isomers are included in the present invention.

[0027] The molecular weights shown in the text refer to the number average molecular weight (M n ) unless otherwise specified. All molecular weight data refer to values obtained by gel permeation chromatography (GPC) as described in the examples.

[0028] When a document is cited within the context of this specification, its entire content is intended to be part of the disclosure of the present invention.

[0029] In a first aspect of the present invention, the following components: (a) at least one silicone urethane (meth)acrylate having: - at least three (meth)acrylate groups, and - no more urethane groups than (meth)acrylate groups, preferably the same number of urethane groups as (meth)acrylate groups; (b) at least one organic (meth)acrylate having no silicon atom; (c) At least one silicone (meth) acrylate having no urethane group; (d) Optionally, at least one curing catalyst; (e) Optionally, at least one additive; (f) Optionally, at least one solvent; A composition comprising or consisting essentially of: - 20 to 70%, preferably 25 to 60%, more preferably 25 to 50% (by weight) of component (a); - 20 to 80%, preferably 30 to 70%, more preferably 40 to 65% (by weight) of component (b); - 1 to 60%, preferably 2 to 40%, more preferably 5 to 25% (by weight) of at least component (c); - 0 to 5%, preferably 0.1 to 3%, more preferably 0.5 to 2.5% (by weight) of component (d); - 0 to 20%, preferably 0 to 10%, more preferably 0 to 5% (by weight) of component (e); - 0 to 10%, preferably 0 to 5%, more preferably 0 to 1% (by weight) of component (f); wherein, based on the total weight of components (a) to (f) and / or based on the total weight of the composition, preferably based on the total weight of the composition, There is provided a composition, characterized in that.

[0030] The silicone urethane (meth) acrylate is - At least three (meth) acrylate groups, and - No more urethane groups than (meth) acrylate groups, preferably exactly the same number of urethane groups as (meth) acrylate groups, Having.

[0031] Preferably, the silicone urethane (meth) acrylate has m (meth) acrylate groups and n urethane groups, where m is an integer of at least 3, preferably 3 to 5, more preferably 4; n is an integer of at least 2, preferably 2 to 4, more preferably 4; However, m ≧ n, preferably m = n.

[0032] Examples of possible combinations of m (meth) acrylate groups and n urethane groups (m; n) include, but are not limited to, (3; 1), (3; 2), (3; 3), (4; 1), (4; 2), (4; 3), (4; 4), (5; 1), (5; 2), (5; 3), (5; 4), (5; 5); (6; 1), (6; 2), (6; 3), (6; 4), (6; 5), or (6; 6); preferably, (3; 2), (3; 3), (4; 2), (4; 3), (4; 4), (5; 2), (5; 3), (5; 4), or (5; 5), particularly preferably (4; 4).

[0033] Preferably, the silicone urethane (meth) acrylate is represented by formula (B), X(-Y) p Formula (B) In the formula, X is a p-valent silicone radical; Y is bonded to the silicon atom of the silicone radical, and in each case, independently, is selected from the group consisting of monovalent organic radicals having at least one urethane group and at least one (meth) acrylate group, preferably, in each case, independently, is selected from the group consisting of monovalent organic radicals having two (meth) acrylate groups and one or two urethane groups, more preferably, in each case, independently, is selected from the group consisting of monovalent organic radicals having two (meth) acrylate groups and two urethane groups; p is an integer of at least 1, preferably 2 to 4, more preferably 2.

[0034] The silicone radical can be linear, branched, cyclic, or a combination thereof. The silicone radical is preferably linear. The silicone radical is particularly preferably a divalent polydimethylsiloxane radical.

[0035] Preferably, the silicone urethane (meth) acrylate contains a unit represented by formula (C), [R a Y b SiO (4-a-b) / 2 formula (C) In the formula, a is an integer and is 0 to 2, preferably 1 or 2; b is an integer and is 1 to 3, preferably 1; However, a + b is 1 to 3; R is, in each case, independently selected from the group consisting of monovalent organic radicals having no urethane group, preferably, in each case, independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 30 carbon atoms, more preferably, a methyl radical; Y is as defined above.

[0036] Preferably, the silicone urethane (meth) acrylate particularly preferably has exactly two units represented by formula (C) defined above, and each of these units has two radicals R and one radical Y, that is, it is particularly preferred that a = 2 and b = 1.

[0037] Preferably, the silicone urethane (meth) acrylate preferably contains a group of formula (A) contained in the radical Y,

Chemical formula

[0038] Examples of the covalent bond represented by the dotted line are bonds to organic radicals such as hydrogen radicals or alkyl radicals or alkylene radicals, which may be linear, branched or cyclic and are optionally interrupted by oxygen atoms. Preferably, at least one of the dotted lines represents a covalent bond to an organic radical having a covalent bond to a silicon atom itself, and the organic radical is preferably a divalent hydrocarbon radical that can be interrupted by an oxygen atom.

[0039] Z 2 in each case is preferably independently selected from the group of divalent saturated or unsaturated linear or branched or cyclic hydrocarbon radicals having 1 to 30 carbon atoms. Z 2 is the residue of a diisocyanate of the formula OCN-Z 2 -CNO (formula (D)). The term "residue of a diisocyanate" is defined herein as the molecular structure of a diisocyanate from which all isocyanate groups have been removed. Examples of suitable diisocyanates are shown below. Z 2 is the residue of a diisocyanate of the formula OCN-Z 2 -CNO, and it is particularly preferably a divalent radical derived from a diisocyanate, and the diisocyanate is IPDI.

[0040] Z 3 in each case is preferably independently selected from the group of (q + 1)-valent saturated or unsaturated linear or branched or cyclic hydrocarbon radicals having 2 to 30 carbon atoms. Z 3 may be the residue of a hydroxy-functional (meth)acrylate of formula (E). [Chemical]

[0041] Examples of suitable hydroxy-functional (meth) acrylates are shown below. Hydroxyethyl acrylate is particularly preferred.

[0042] Preferably, the silicone urethane (meth) acrylate is represented by formula (F), M m1 M UA m2 M A m3 D d1 D UA d2 D A d3 T t Q q Formula (F), wherein, M = [R3SiO 1 / 2 ; M UA = [R2(R UA )SiO 1 / 2 ; M A = [R2(R A )SiO 1 / 2 ; D = [R2SiO 2 / 2 ; D UA = [R(R UA )SiO 2 / 2 ; D A = [R(R A )SiO 2 / 2 ; T = [RSiO 3 / 2 ; Q = [SiO 4 / 2 ; and m1 is an integer from 0 to 32, preferably from 0 to 22, more preferably 0; m2 is an integer from 0 to 32, preferably from 1 to 10, more preferably 2; m3 is an integer from 0 to 32, preferably from 0 to 22, more preferably 0; d1 is an integer from 1 to 1000, preferably from 5 to 500, more preferably from 10 to 400; d2 is an integer from 0 to 10, preferably from 0 to 5, more preferably 0; d3 is an integer from 0 to 10, preferably from 0 to 5, more preferably 0; t is an integer from 0 to 10, preferably from 0 to 5, more preferably from 1 to 5; q is an integer from 0 to 10, preferably from 0 to 5, more preferably from 1 to 5; However, m1 + m2 + m3 is at least 2, preferably from 2 to 20, more preferably from 2 to 10; m2 + d2 is at least 1, preferably from 2 to 10, more preferably from 2 to 6; R is, in each case independently, selected from the group consisting of monovalent organic radicals having no urethane group or (meth)acrylate group, preferably, in each case independently, selected from the group consisting of monovalent hydrocarbon radicals having 1 to 30 carbon atoms, more preferably a methyl radical; R UA is, in each case independently, selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group and at least one urethane group, preferably, in each case independently, selected from the group consisting of monovalent organic radicals having two (meth)acrylate groups and one or two urethane groups, more preferably, in each case independently, selected from the group consisting of monovalent organic radicals represented by formula (G),

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0043] The radical R UA or Y is each more preferably represented by at least one of formulas (M), (N), (O) and (P).

Chemical formula

Chemical formula

[0044] Preferably, the following applies to the silicone urethane (meth)acrylate according to formula (F). m1 = d2 = t = q = 0; m2 = 2; and d1 is from 1 to 1000, preferably from 5 to 500, more preferably from 10 to 400, even more preferably from 20 to 100.

[0045] The (meth)acrylate group of the silicone urethane (meth)acrylate is preferably an acrylate group.

[0046] Preferably, the silicone urethane (meth)acrylate of the present invention does not contain a group containing a moiety of the formula -(C=O)-NH- other than the urethane group.

[0047] The silicone urethane (meth)acrylate preferably has a viscosity at 25 °C of less than 200 Pa·s, preferably 0.5 to 150 Pa·s, more preferably 10 to 100 Pa·s. The glass transition temperature is preferably determined as described in the examples.

[0048] The silicone urethane (meth)acrylate has a weight average molecular weight M of 1000 to 20000 g / mol, preferably 2000 to 15000 g / mol, more preferably 3000 to 10000 g / mol w Preferably. The weight average molecular weight is preferably determined as described in the examples.

[0049] The silicone urethane (meth)acrylate has a number average molecular weight M of 1000 to 10000 g / mol, preferably 1500 to 7500 g / mol, more preferably 2000 to 5000 g / mol n Preferably. The weight average molecular weight is preferably determined as described in the examples.

[0050] The cured silicone urethane (meth)acrylate preferably has a glass transition temperature (T g ) of less than 100 °C, preferably 20 to 80 °C, more preferably 40 to 70 °C. The glass transition temperature is preferably determined by differential scanning calorimetry (DSC) according to DSC method DIN 53765 at a heating rate of 10 K / min.

[0051] The silicone urethane (meth)acrylate comprises the following steps: (1) Reacting at least one hydroxy-functional silicone (meth)acrylate with at least one diisocyanate under the formation of at least one urethane group to obtain an isocyanate-functional prepolymer; (2) reacting at least one hydroxy-functional (meth)acrylate with the isocyanate-functional prepolymer obtained in step (1) under formation of at least one urethane bond It can be prepared by a method comprising or consisting of.

[0052] Those skilled in the art know how to carry out the reaction and select appropriate reaction conditions to achieve a high yield, as described, for example, in Korean Patent Application Publication No. 20170128955 and Chinese Patent Application Publication No. 106519182. For example, the molar ratio of hydroxyl groups to isocyanato groups is preferably about 1:2 in step (1) and about 1:1 in step (2).

[0053] Surprisingly, an alternative method for producing silicone urethane (meth)acrylate is much more advantageous. According to this method, a hydroxy-functional silicone (meth)acrylate is reacted with an isocyanate-functional urethane (meth)acrylate. By applying this method, the viscosity can be further reduced.

[0054] Thus, in a preferred method for preparing silicone urethane (meth)acrylate, the silicone urethane (meth)acrylate is formed by the reaction of at least one hydroxy-functional silicone (meth)acrylate and at least one isocyanate-functional urethane (meth)acrylate.

[0055] The reaction between hydroxy-functional silicone (meth)acrylate and isocyanate-functional urethane (meth)acrylate involves the reaction of free NCO groups with hydroxyl groups and has already been frequently described (WO 2010 / 072439 A1 and the references cited therein). This reaction can be carried out with or without a solvent. This is generally carried out in the temperature range of 40 °C to 80 °C. The reaction usually takes 4 to 8 hours. This can be advantageously catalyzed by common catalysts known in urethane chemistry, such as organometallic compounds and tertiary amines. Examples of suitable organometallic compounds are dibutyltin dilaurate (DBTL), dibutyltin dineodecanoate, zinc octoate, and bismuth neodecanoate. Examples of suitable tertiary amines are triethylamine or diazabicyclooctane. Suitable reaction assemblies include all conventional devices, tanks, static mixers, extruders, etc., preferably assemblies having a mixing or stirring function. The NCO / OH ratio is typically 2:1 to 1:2, preferably 1.5:1 to 1:1.5, more preferably 1:1. The reaction can be carried out in the presence of a solvent, preferably without the presence of a solvent. A suitable solvent is, for example, acetone. In order to avoid the polymerization of (meth)acrylate groups, it may be advantageous to carry out the reaction in the presence of an antioxidant / polymerization inhibitor. The inhibitor can be added to the reaction mixture together with the isocyanate-functional urethane (meth)acrylate that can react with the hydroxyl groups of the hydroxy-functional silicone (meth)acrylate. If a solvent is used, the solvent may preferably be removed after completion of the reaction, preferably under vacuum, or after the preparation of the composition according to the invention.

[0056] Examples of hydroxy-functional silicone (meth) acrylates that can be used to prepare the silicone urethane (meth) acrylate of the present invention are also known to those skilled in the art. The hydroxy-functional silicone (meth) acrylate is preferably formed by the reaction of at least one epoxy-functional silicone with (meth) acrylic acid and / or at least one hydroxy-functional (meth) acrylate. The hydroxy-functional silicone (meth) acrylate is more preferably formed by the reaction of at least one epoxy-functional silicone with methacrylic acid and / or acrylic acid, particularly acrylic acid. This is described in U.S. Patent No. 4,978,726 and the references cited therein. Examples of suitable hydroxy-functional (meth) acrylates that can be used are the same as those that can be used in the synthesis of the isocyanate-functional urethane (meth) acrylate described below.

[0057] Examples of isocyanate-functional urethane (meth) acrylates that can be used to prepare the silicone urethane (meth) acrylate of the present invention are also known from the prior art and are described, for example, in WO 2010 / 072439 A1 and WO 2010 / 115644 A1. Commercially available isocyanate-functional urethane (meth) acrylates that can be used are, for example, VESTANAT® EP DC-1241 (available from Evonik Industries AG, Germany). The isocyanate-functional urethane (meth) acrylate can be prepared by the reaction of a diisocyanate with a hydroxy-functional (meth) acrylate under the formation of a urethane bond, as described in WO 2010 / 072439 A1.

[0058] Preferred diisocyanates are aliphatic, cycloaliphatic, araliphatic, i.e., aryl-substituted aliphatic diisocyanates (e.g., Houben-Weyl, Methoden der organischen Chemie, Volume 14 / 2, pages 61-70, and W.(described in the paper by Siefken in Justus Liebigs Annalen der Chemie 562, pages 75 - 136), for example, 1,2 - ethylenediisocyanate, 1,4 - tetramethylenediisocyanate, 1,6 - hexamethylenediisocyanate (HDI), 2,2,4 - trimethyl - 1,6 - hexamethylenediisocyanate (TMDI), 2,4,4 - trimethyl - 1,6 - hexamethylenediisocyanate (TMDI), 1,9 - diisocyanato - 5 - methylnonane, 1,8 - diisocyanato - 2,4 - dimethyloctane, 1,12 - dodecanediisocyanate, ω,ω’ - diisocyanatodipropyl ether, cyclobutene 1,3 - diisocyanate, cyclohexane 1,3 - diisocyanate, cyclohexane 1,4 - diisocyanate, 3 - isocyanato - methyl - 3,5,5 - trimethylcyclo - hexyl isocyanate (isophorone diisocyanate, IPDI), 1,4 - diisocyanatomethyl - 2,3,5,6 - tetramethylcyclohexane, decahydro - 8 - methyl - (1,4 - methano - naphthalene) - 2,5 - ilenedimethylene diisocyanate, decahydro - 8 - methyl - (1,4 - methano - naphthalene) - 3,5 - ilenedimethylene diisocyanate, hexahydro - 4,7 - methanoindane - 1,5 - ilenedimethylene diisocyanate, hexahydro - 4,7 - methanoindane - 2,5 - ilenedimethylene diisocyanate, hexahydro - 4,7 - methanoindane - 1,6 - ilenedimethylene diisocyanate, hexahydro - 4,7 - methanoindane - 2,5 - ilenedimethylene diisocyanate, hexahydro - 4,7 - methanoindane - 1,5 - diisocyanate, hexahydro - 4,7 - methanoindane - 2,5 - diisocyanate, hexahydro - 4,7 - methanoindane - 1,6 - diisocyanate, hexahydro - 4,7 - methanoindane - 2,6 - diisocyanate, 2,4 - hexahydrotoluene diisocyanate, 2,6 - hexahydrotoluene diisocyanate, 4,4’ - methylenedicyclohexyl diisocyanate (4,4’ - H. 12 MDI), 2,2’ - methylenedi - cyclohexyl diisocyanate (2,2’ - H 12MDI), 2,4-methylene-di-cyclohexyl diisocyanate (2,4-H 12 MDI) or other mixtures, 4,4'-diisocyanato-3,3',5,5'-tetramethyldicyclohexylmethane, 4,4'-diisocyanato-2,2',3,3',5,5',6,6'-octamethyldicyclohexylmethane, ω,ω'-diisocyanato-1,4-diethylbenzene, 1,4-diisocyanatomethyl-2,3,5,6-tetramethylbenzene, 2-methyl-1,5-diisocyanatopentane (MPDI), 2-ethyl-1,4-diisocyanatobutane, 1,10-diisocyanatodecane, 1,5-diisocyanatohexane, 1,3-diisocyanatomethylcyclohexane, 1,4-diisocyanatomethylcyclohexane, and any desired mixture of these compounds. Further preferred isocyanates are described in the aforementioned paper in Justus Liebigs Annalen der Chemie on page 122 f. 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (NBDI) and / or 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (NBDI) are also preferred. Particularly preferred are industrially readily available aliphatic and cycloaliphatic diisocyanates such as IPDI, HDI and H 12 MDI, and their isomer mixtures, especially IPDI is used. The diisocyanates are embodiments of the diisocyanates of formula (D) above.

[0059] Preferred hydroxy-functional (meth)acrylates are all compounds having at least one methacrylate or acrylate functional group as well as exactly one hydroxyl group. Further components can be aliphatic, cycloaliphatic, aromatic or heterocyclic alkyl groups. Oligomers or polymers are also conceivable. Readily available products such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycerol diacrylate, pentaerythritol triacrylate, trimethylolpropane diacrylate, glycerol dimethacrylate, pentaerythritol trimethacrylate and trimethylolpropane dimethacrylate, as well as hydroxyl-ethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether and hydroxyhexyl vinyl ether are also preferred. Hydroxyethyl acrylate is particularly preferred. It is also possible to use mixtures of two or more of these hydroxy-functional (meth)acrylates. Said hydroxy-functional (meth)acrylates are embodiments of the hydroxy-functional (meth)acrylates of formula (E) above.

[0060] The composition according to the invention comprises the following components: (a) at least one silicone urethane (meth)acrylate according to the invention and / or prepared by the method according to the invention, (b) optionally at least one organic (meth)acrylate having no silicon atom; (c) optionally at least one silicone (meth)acrylate having no urethane group; (d) optionally at least one curing catalyst; (e) optionally at least one additive; (f) optionally at least one solvent and comprises or (essentially) consists of the same.

[0061] The composition is as follows, based on the total weight of components (a) to (f) and / or based on the total weight of the composition, preferably based on the total weight of the composition: - 20 to 70%, preferably 25 to 60%, more preferably 25 to 50% by weight of component (a); - 20 to 80%, preferably 30 to 70%, more preferably 40 to 65% by weight of component (b); - at least 1 to 60%, preferably 2 to 40%, more preferably 5 to 25% by weight of component (c); - 0 to 5%, preferably 0.1 to 3%, more preferably 0.5 to 2.5% by weight of component (d); - 0 to 20%, preferably 0 to 10%, more preferably 0 to 5% by weight of component (e); - 0 to 10%, preferably 0 to 5%, more preferably 0 to 1% by weight of component (f); comprises or (essentially) consists of.

[0062] One or more silicone urethane (meth)acrylates according to the invention are also denoted herein as component (a).

[0063] The amount of silicone urethane (meth)acrylate (component (a)) present in the composition of the invention is 5 to 100% by weight, preferably 5 to 20% by weight, more preferably 10 to 20% by weight, based on the total weight of components (a) to (e) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0064] The composition according to the present invention preferably further comprises component (b). Component (b) can be used as a reactive diluent for reducing and adjusting the viscosity of the composition. Alternatively, component (b) can be used as a crosslinking agent. Component (b) of the composition consists of one or more organic (meth)acrylates having no silicon atom. Therefore, the organic (meth)acrylate does not contain a silicon atom. The organic (meth)acrylate preferably consists only of the elements carbon, hydrogen, oxygen and nitrogen. Further, the organic (meth)acrylate preferably has 2 to 6 (meth)acrylate groups. Such compounds are described in European Coatings Tech Files, Patrick Glockner et al., "Radiation Curing: Coatings and Printing Inks", 2008, Vincentz Network, Hanover, Germany.

[0065] Particularly preferred organic (meth)acrylates are disclosed in WO 2016 / 096595 A1 and WO 2018 / 001687 A1. Examples of organic (meth)acrylates can be selected from the group consisting of trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), isobornyl acrylate (IBOA), lauryl acrylate, 1,6 - hexanediol diacrylate (HDDA), tridecyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, propoxylated glyceryl triacrylate, polyethylene glycol diacrylate, and their ethoxylated and / or propoxylated derivatives, but are not limited thereto.

[0066] Suitable organic (meth)acrylates also include those commercially available under the trade names Ebecryl® TMPTA (Allnex SA, Germany), Ebecryl® OTA480 (propoxylated glyceryl triacrylate, Allnex SA, Germany), Ebecryl® TPGDA (Allnex SA, Germany), Ebecryl® DPGDA (Allnex SA, Germany), Ebecryl® 892 (Allnex SA, Germany), Ebecryl® 11(M w polyethylene glycol 600 diacrylate having 700 g / mol, Allnex SA, Germany), Ebecryl® 45 (Allnex SA, Germany), PETIA (mixture of pentaerythritol tri- and tetraacrylate, Allnex SA, Germany), Ebecryl® 150 (bisphenol A derivative diacrylate, Allnex SA, Germany), Ebecryl® 605 (mixture of 80% bisphenol A diepoxyacrylate and 20% TPGDA, Allnex SA, Germany), Ebecryl® 40 (ethoxylated and propoxylated (total 1.2 propylene oxide units and 5 ethylene oxide units) pentaerythritol tetraacrylate, Allnex SA, Germany), Laromer® TMPTA (BASF, Germany), Miramer® M200 (HDDA, Rahn AG, Germany), Miramer® M220 (TPGDA, Rahn AG, Germany), Miramer® 3130 (ethoxylated trimethylolpropane triacrylate (total 3 ethylene oxide units), Rahn AG, Germany), SR 415 (ethoxylated (total 20 ethylene oxide units) trimethylolpropane triacrylate, Sartomer, France), SR 489 (tridecyl acrylate, Sartomer, France).

[0067] Suitable organic (meth)acrylates are also commercially available from Evonik Industries AG (Germany) in the VISIOMER® product line. Preferred compounds are glycerol formal methacrylate (VISIOMER® GLYFOMA), diurethane dimethacrylate (VISIOMER® HEMA TMDI), butyl diglycol methacrylate (VISIOMER® BDGMA), polyethylene glycol 200 dimethacrylate (VISIOMER® PEG200DMA), trimethylolpropane methacrylate (VISIOMER® TMPTMA), tetrahydrofurfuryl methacrylate (VISIOMER® THFMA), isobornyl methacrylate (VISIOMER® Terra IBOMA), isobornyl acrylate (VISIOMER® IBOA), methacrylic acid ester of a fatty alcohol with an average carbon number of 13.0 (VISIOMER® Terra C13-MA), or methacrylic acid ester of a fatty alcohol with an average carbon number of 17.4 (VISIOMER® Terra C17.4-MA).

[0068] The composition of the present invention more preferably contains an organic (meth)acrylate selected from the group consisting of isobornyl methacrylate (VISIOMER® Terra IBOMA), isobornyl acrylate (VISIOMER® IBOA), lauryl acrylate, Ebecryl® 45, hexanediol diacrylate, and trimethylolpropane triacrylate.

[0069] The (meth)acrylate group of the organic (meth)acrylate (component (b)) silicone (meth)acrylate is preferably an acrylate group.

[0070] The (meth)acrylate group of the organic (meth)acrylate (component (b)) silicone (meth)acrylate is also preferably a (meth)acrylate group.

[0071] The amount of the organic (meth)acrylate (component (b)) present in the composition of the present invention is preferably 0 to 60% by weight, more preferably 0 to 30% by weight, still more preferably 5 to 15% by weight, based on the total weight of components (a) to (e) and / or based on the total weight of the composition.

[0072] The composition according to the present invention preferably contains component (c). Component (c) consists of at least one silicone (meth)acrylate having no urethane group. Therefore, the silicone (meth)acrylate does not contain a urethane group.

[0073] Preferably, at least one silicone (meth)acrylate of component (c) is represented by formula (Q) and / or at least one silicone (meth)acrylate of component (c) is represented by formula (S). M A m1 D d1 Formula (Q); In the formula, M A =[R2(R A )SiO 1 / 2 ; D = [R2SiO 2 / 2 , and; m1 is an integer of 2; d1 is an integer of 1 to 10000, preferably 50 to 5000, more preferably 70 to 2000; R is independently selected in each case from the group consisting of monovalent organic radicals having no urethane group or (meth)acrylate group. Preferably, it is independently selected in each case from the group consisting of monovalent hydrocarbon radicals having 1 to 30 carbon atoms. More preferably, it is a methyl radical. R A is independently selected in each case from the group consisting of monovalent organic radicals having at least one (meth)acrylate group but no urethane group. Preferably, in each case, independently, the formula (R) [Chemical formula] is selected from the group consisting of monovalent radicals represented by; x1 is as defined above; x4 is an integer, 0 or 1, preferably 0; R 6 is, in each case, independently, selected from the group consisting of monovalent hydrocarbon radicals having 1 to 6 carbon atoms; Preferably, it is an ethyl radical; R 7 is, in each case, independently, selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group but no urethane group; Preferably, in each case, independently, it is selected from the monovalent radicals of formula (H) defined above; M m1 D d1 D A d2 D AC d3 Formula (S); In the formula, M = [R3SiO 1 / 2 ; D = [R2SiO 2 / 2 ; D A = [R(R A )SiO 2 / 2 ; D AC = [R(R AC )SiO 2 / 2 ; In the formula, R, m1 and d1 are as defined above for formula (Q); d2 is an integer from 1 to 20, preferably 2 to 10, more preferably 3 to 8; d3 is an integer from 0 to 3, preferably 0 to 2, more preferably 0 to 1; R Ais, in each case, independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group but no urethane group; Preferably, in each case, independently selected from the group consisting of monovalent radicals represented by formula (K) or (L); More preferably, in each case, independently selected from the group consisting of monovalent radicals represented by formula (K); [Chemical formula] [Chemical formula] wherein x1 and R 4 are as defined above; R AC is, in each case, independently selected from the group consisting of monovalent organic radicals having at least one carboxylic acid ester group but no (meth)acrylate group and no urethane group; Preferably, in each case, independently selected from the group consisting of monovalent radicals represented by formula (T) or (U), [Chemical formula] [Chemical formula] wherein x1 is as defined above; R 5 is, in each case, independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 22 carbon atoms; Preferably it is a methyl radical.

[0074] At least one silicone (meth)acrylate of component (c) represented by formula (Q) is shown herein as component (c1). At least one silicone (meth)acrylate of component (c) represented by formula (S) is shown herein as component (c2). Accordingly, component (c) consists of component (c1) and / or component (c2), component (c1) consists of at least one silicone (meth)acrylate represented by formula (Q), and component (c2) consists of at least one silicone (meth)acrylate represented by formula (S).

[0075] Examples of the silicone (meth)acrylate (component (c1)) according to formula (Q) are known to those skilled in the art and can be prepared as described, for example, in EP 0940422 A1.

[0076] Examples of the silicone (meth)acrylate (component (c2)) according to formula (S) are also known to those skilled in the art and can be prepared as described, for example, in EP 3168273 A1 and WO 2017187030 A1.

[0077] The amount of the silicone (meth)acrylate (component (c)) present in the composition of the present invention is preferably 0 to 95% by weight, preferably 65 to 85% by weight, more preferably 70 to 80% by weight, based on the total weight of components (a) to (e) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0078] The amount of the silicone (meth)acrylate (component (c1)) according to formula (Q) present in the composition of the present invention is particularly preferably 0 to 95% by weight, preferably 65 to 85% by weight, more preferably 70 to 80% by weight, based on the total weight of components (a) to (e) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0079] The amount of the silicone (meth)acrylate (constituent (c2)) according to formula (S) present in the composition of the present invention is preferably 0 to 95% by weight, preferably 65 to 85% by weight, more preferably 70 to 80% by weight, based on the total weight of constituents (a) to (e) and / or based on the total weight of the composition, particularly preferably based on the total weight of the composition.

[0080] The (meth)acrylate group of the silicone (meth)acrylate (constituent (c1)) represented by formula (Q) is preferably an acrylate group. Similarly, the (meth)acrylate group of the silicone (meth)acrylate (constituent (c2)) represented by formula (S) is preferably an acrylate group. More preferably, the (meth)acrylate group of the silicone (meth)acrylate (constituent (c1)) represented by formula (Q) and the (meth)acrylate group of the silicone (meth)acrylate (constituent (c1)) represented by formula (S) are acrylate groups.

[0081] Particularly preferably, the (meth)acrylate groups of constituents (a), (b) and (c) (for example, constituents (c1) and (c2)) are acrylate groups.

[0082] Particularly preferably, the (meth)acrylate groups of constituents (a) and (c) (for example, (c1) and (c2)) are acrylate groups, and the (meth)acrylate group of constituent (b) is a (meth)acrylate group.

[0083] Constituent (d) of the composition according to the present invention consists of one or more curing catalysts. The curing catalyst is preferably a compound that generates reactive species, such as free radicals, cations or anions, more preferably radicals, when exposed to an external trigger such as actinic rays, preferably UV light and / or visible light, or heat. Therefore, the curing catalyst may be a photocuring catalyst (photoinitiator) or a thermocuring catalyst (thermosetting catalyst).

[0084] It may be advantageous to have one or more thermosetting catalysts present in the composition of the present invention. A thermosetting catalyst is a compound that generates reactive species, such as free radicals, cations or anions when exposed to heat. The thermosetting catalyst preferably comprises organic peroxides such as 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (e.g., LUPEROX 101 (registered trademark)), dilauroyl peroxide (e.g., LUPEROX LP (registered trademark)), dibenzoyl peroxide (e.g., LUPEROX A98 (registered trademark)), bis(tert-butyldioxyisopropyl)benzene (e.g., VulCUP R (registered trademark)). Such organic peroxides are available from various sources including, but not limited to, Arkema (France). Desirable examples include ketone peroxides such as methyl ethyl ketone peroxide, diacyl peroxides such as benzoyl peroxide, hydroperoxides such as cumene hydroperoxide, as well as peroxyketals, dialkyl peroxides, peroxydicarbonates and peroxy esters. Examples of thermosetting catalysts also include inorganic peroxides such as peroxydisulfates including sodium persulfate (Na2S2O8), potassium persulfate (K2S2O8), and ammonium persulfate ((NH4)2S2O8). Examples of thermosetting catalysts further include azobisisobutyronitrile (AIBN).

[0085] It may be advantageous to have one or more photoinitiators present in the composition of the present invention. A photoinitiator is a compound that generates reactive species, such as free radicals, cations or anions, upon exposure to actinic radiation, preferably UV light or visible light, more preferably UV light. Any suitable photoinitiator, including Norrish type I and Norrish type II photoinitiators and commonly used UV photoinitiators, such as acetophenone (e.g., diethoxyacetophenone), phosphine oxide diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (PPO), Irgacure 369, etc. (see, for example, U.S. Patent No. 9,453,142 to Rolland et al.), may be present in the composition of the present invention, but are not limited thereto. Preferred photoinitiators according to the present invention are those that generate free radicals. The most preferred photoinitiator is bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, available under the trade name OMNIRAD® 819 from IGM resins (formerly known as IRGACURE® 819 from BASF SE). Other photoinitiators that can be used in the composition of the present invention are available under the product names OMNIRAD® TPO (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide) and OMNIRAD® TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate) from IGM resins. Particularly preferred are Norrish type 1 photoinitiators, such as benzophenone, benzoin, α-hydroxyalkylphenone, acylphosphine oxide, or derivatives thereof. Conventional photoinitiators are described, for example, in "A Compilation of Photoinitiators Commercially available for UV today" (K. Dietliker, SITA Technology Ltd., London 2002).

[0086] The amount of the curing catalyst (constituent (d)) present in the composition of the present invention is preferably 0 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.5 to 2.5% by weight, based on the total weight of the constituents (a) to (e) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0087] Constituent (e) of the composition according to the present invention consists of one or more additives.

[0088] Constituent (e) can contain solid particles suspended or dispersed therein as the additive(s). Depending on the final product to be produced, any suitable solid particles can be used. The particles can be metals, organic / polymer, inorganic or composite materials, or mixtures thereof. The particles can be non-conductive, semi-conductive, or conductive (including metal and non-metal or polymer conductors). The particles can be magnetic, ferromagnetic, paramagnetic or non-magnetic. The particles can be of any suitable shape including spherical, elliptical, cylindrical, etc. The particles can be of any suitable size (e.g., an average diameter in the range of 1 nm to 200 μm). The particles can contain activator or detectable compounds, which may also be provided dissolved / solubilized in the composition of the present invention. For example, magnetic or paramagnetic particles or nanoparticles can be used.

[0089] Constituent (e) can also contain pigments, dyes, active compounds, detectable compounds (e.g., fluorescence, phosphorescence) as additives, depending on the specific purpose of the product to be produced.

[0090] Component (e) particularly preferably contains a non-reactive pigment or dye that absorbs light as an additive(s). Suitable examples of such light absorbers include: (i) titanium dioxide (e.g., included in an amount of 0.05 or 0.1 to 1 or 5 percent (by weight)), (ii) carbon black (e.g., included in an amount of 0.05 or 0.1 to 1 or 5 percent (by weight)), and / or organic ultraviolet absorbers (UV blockers) such as hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, thiophene, and / or benzotriazole ultraviolet absorbers (e.g., Mayzo BLS1326) (e.g., included in an amount of 0.001 or 0.005 to 1, 2 or 4 percent (by weight)), but are not limited thereto. Examples of suitable organic ultraviolet absorbers include those described in U.S. Patent Nos. 3,213,058; 6,916,867; 7,157,586; and 7,695,643, but are not limited thereto; the disclosures of which are incorporated herein by reference. A further example of a suitable organic ultraviolet absorber is 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (BBOT).

[0091] When the composition contains component (d) that contains a thermosetting catalyst, component (e) is also present and preferably contains a curing accelerator for thermosetting. Examples of such curing accelerators include metal organic acid salts such as cobalt naphthenate, and N-substituted aromatic amines such as N,N-dimethylaniline and N,N-dimethyl-p-toluidine.

[0092] When the composition contains the component (d) containing a photoinitiator, it is preferable that the component (e) also be present and contain a photosensitizer. Examples of such photosensitizers include, but are not limited to, amines such as n-butylamine, triethylamine, N-methyldiethanolamine, piperidine, N,N-dimethylaniline and triethylenetetramine, sulfur compounds such as S-benzyl-isothiouronium-p-toluenesulfinate, nitriles such as N,N-dimethyl-p-aminobenzonitrile, and phosphorus compounds such as sodium diethylthiophosphate.

[0093] The composition according to the invention may contain any suitable filler as an additive (constituent (e)), depending on the desired properties in the parts or objects to be produced. Thus, the filler can be solid or liquid, organic or inorganic, and includes, but is not limited to, reactive and non-reactive rubbers: siloxanes, acrylonitrile-butadiene rubber; reactive and non-reactive thermoplastics (including, but not limited to, poly(etherimide), maleimide-styrene terpolymer, polyacrylate, polysulfone, and polyethersulfone, etc.) inorganic fillers, such as silicates (talc, clay, silica, mica, etc.), glass, carbon nanotubes, graphene, cellulose nanocrystals, etc., including all the combinations mentioned above. Suitable fillers include, but are not limited to, reinforcing agents, such as core-shell rubber. The filler is preferably selected from inorganic particles, more preferably selected from carbon black and / or silica. Most preferably, silica functionalized with a methacrylate group is present as a filler in the composition according to the invention. Suitable silica functionalized with a methacrylate group is available, for example, under the trade names AEROSIL® 701, AEROSIL® 711, AEROSIL® R 7200, and AEROSIL® R 8200 from Evonik Industries AG (Germany). The amount of filler present in the composition of the invention is preferably 0 to 20% (by weight), preferably 0 to 10% (by weight), more preferably 0 to 5% (by weight), based on the total weight of constituents (a) to (e) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0094] The composition according to the present invention preferably contains a polymerization inhibitor and / or an antioxidant as additive(s) (constituent(s) (e)). By using a polymerization inhibitor and / or an antioxidant, polymerization of the composition during its preparation and / or its storage can be prevented. Suitable polymerization inhibitors are, for example, 2,6-di-tert-butyl-4-methylphenol, catechol, 4-methoxyphenol, 4-tert-butyloxyphenol, 4-benzyloxyphenol, naphthol, phenothiazine, 10-10-dimethyl-9,10-dihydroacridine, bis-[2-hydroxy-5-methyl-3-cyclohexylphenyl]-methane, bis-[2-hydroxy-5-methyl-3-tert-butylphenyl]-methane, hydroquinone, pyrogallol, 3,4-dihydroxy-1-tert-butylphenol, 4-methoxy-2(3)-tert-butylphenol (BHA), BHA combined with bis-[2-carboxyethyl]-sulfide (TDPA), 4-methyl-2,6-di-tert-butylphenol (BHT), bis-[4-hydroxy-2-methyl-5-tert. -butylphenyl]-sulfide, 4-butylmercaptomethyl-2,6-di-tert-butylphenol, dioctadecyl ester of 4-hydroxy-3,5-di-tert-butylphenylmethanesulfonic acid, 2,5-dihydroxytoluene, 2,5-dihydroxy-1-tert-butylbenzene, 2,5-dihydroxy-1,4-di-tert.-butylbenzene, 3,4-dihydroxy-1-tert.-butylbenzene, 2,3-dimethyl-1,4-bis-[3,4-dihydroxyphenyl]-butane, 2,2’-thiobis-(4-tert-octylphenol), (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), and also TEMPO derivatives such as, for example, 4-hydroxy-TEMPO. A preferred polymerization inhibitor is 2,6-di-tert-butyl-4-methylphenol (BHT) sold under the trade name IONOL® CP by Oxiris Chemicals S.A. The amount of the polymerization inhibitor present in the composition of the present invention is preferably from 0.001 to 1% by weight, more preferably from 0.01 to 0.5% by weight, based on the total composition.

[0095] The total amount of the additive (constituent (e)) present in the composition of the present invention is preferably 0 to 20% (by weight), preferably 0 to 10% (by weight), more preferably 0 to 5% (by weight) based on the total weight of the constituents (a) to (e) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0096] Constituent (f) of the composition according to the present invention consists of one or more solvents. Examples of the solvent include, but are not limited to, aprotic solvents, preferably acetone, tetrahydrofuran (THF), dimethylformamide (DMF), acetonitrile (MeCN) or dimethyl sulfoxide (DMSO), more preferably acetone. However, it is preferable that the composition according to the present invention is essentially free of solvents. Therefore, the amount of the solvent present in the composition of the present invention is preferably 0 to 10% (by weight), preferably 0 to 5% (by weight), more preferably 0 to 1% (by weight) based on the total weight of the constituents (a) to (e) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0097] The composition according to the present invention is preferably used to produce a release coating, a protective film, or a protective coating by curing the composition.

[0098] Accordingly, the composition is curable, preferably curable by a radical reaction, and the radical reaction is preferably initiated thermally, by UV radiation and / or electron beam. The composition according to the invention is three-dimensionally crosslinked by free radicals and can be thermally cured within a very short time, for example by the addition of peroxides or under the influence of high-energy radiation such as UV or electron beam, to form a mechanically and chemically resistant layer which also has the desired non-sticking and adhesive properties when an appropriate formulation of the composition according to the invention is provided. When the radiation used is UV radiation, the crosslinking / curing is preferably carried out in the presence of a photoinitiator and / or photosensitizer. Preferred are Norrish type 1 photoinitiators such as benzophenone, benzoin, α-hydroxyalkylphenone, acylphosphine oxide, or derivatives thereof. Conventional photoinitiators are described, for example, in "A Compilation of Photoinitiators Commercially available for UV today" (K. Dietliker, SITA Technology Ltd., London 2002). Preferred compositions according to the invention contain photoinitiators and / or photosensitizers in a mass ratio of 0.01% to 10%, in particular 0.1% to 5%, based on the total mass of the composition. The photoinitiator and / or photosensitizer is preferably soluble in the composition according to the invention, more preferably soluble in a mass ratio of 0.01% to 10%, in particular 0.1% to 5%, based on the total mass of the composition.

[0099] The composition according to the invention can be prepared by any suitable process, for example, by mixing component (a) with one or more optional components (b) to (f) in any order. The solvent (component (f)) is mainly used to reduce the viscosity of the composition and facilitate the mixing of the components. Component (f) facilitates the production and application of the composition. However, it is generally preferred to provide a composition that is essentially free of solvent, i.e., essentially free of component (f). Therefore, it is preferred to (essentially) remove the solvent (component (f)) from the composition at some point after or during its preparation.

[0100] Accordingly, a further aspect of the invention is the following steps: (i) preparing a mixture of component (a) and component (f); (ii) preparing a mixture by adding at least one of components (b) to (e), preferably components (b) and / or (c), to the mixture of step (i); (iii) (essentially) removing component (f) from the mixture of step (ii); (iv) optionally, preparing a mixture by adding at least one of components (b) to (e) to the mixture of step (iii) if said components were not added in step (ii), which is a method for preparing a composition according to the invention, comprising or consisting of.

[0101] Process steps (i) to (iv) are carried out in a given order. However, they may be interrupted by additional intermediate process steps. In addition to or instead of the solvent component (g), it is also possible to use a reactive diluent (component (b)). The preparation of the said mixture can be carried out at room temperature or at an elevated temperature. Mixing can be carried out using conventional mixing devices, for example a speed mixer.

[0102] The composition according to the present invention can be used in various fields. The composition is particularly suitable for use in the production of release coatings, protective films, and protective coatings.

[0103] Accordingly, a further aspect of the present invention is a release coating, protective film, or protective coating obtainable by curing the composition according to the present invention.

[0104] It is preferred to produce a release coating using the composition according to the present invention. Release coatings (often also called non-stick coatings) are known from the prior art. They are used in many diverse ways for producing labels, adhesive tapes, or hygiene articles. Release coatings are characterized by having low adhesiveness even in contact with an adhesive and are composed of radiation-curable silicone. Typically, two mechanisms are used for curing functional silicone. In the case of cationic curing, epoxy-functional organosiloxanes are polymerized using a photoinitiator that releases an acid upon irradiation. In the case of free radical curing, silicone (meth)acrylates are polymerized using a photoinitiator that forms radicals upon irradiation.

[0105] The composition of the present invention exhibits low viscosity, a high-speed photocuring reaction, and good mechanical properties, particularly with regard to tensile breaking strength and elongation at break.

[0106] The composition used in the present invention has the advantage that it can be processed at room temperature below 50°C, preferably below 25°C. This is because the viscosity of the composition at the processing temperature is preferably less than 20 Pa·s.

[0107] The composition used in the present invention has the advantage that it can be processed without the presence of a solvent. Thus, no organic volatile substances are produced during the additive manufacturing process.

[0108] The composition used in the present invention further has the advantage that it can be produced in a simple manner.

[0109] The composition used in the present invention has the advantage that it can contain fillers which result in better properties, in particular better tensile breaking strength and elongation at break.

[0110] The composition used in the present invention has the advantage that it can contain fillers which result in better properties, in particular good scratch resistance and good release properties.

[0111] The composition used in the present invention contains a polymer (reaction product) having a low T g By using these compositions, there is a further advantage that products having an elastomer or one or more properties typical of an elastomer, for example an elongation at break preferably exceeding 40%, more preferably exceeding 60%, most preferably exceeding 100%, can be obtained by additive manufacturing.

[0112] A further aspect of the present invention is a process for preparing a release coating, protective film or protective coating, preferably the following indirectly or directly consecutive steps: a. applying the composition to a surface; b. curing the composition, preferably by irradiation with UV radiation is included.

[0113] Therefore, it is preferred that a release coating, protective film or protective coating can be obtained by this method.

[0114] A suitable UV radiation source for curing the composition according to the present invention is an optionally doped medium pressure mercury vapor lamp, or a low pressure mercury vapor lamp, a UV-LED lamp, or a so-called excimer emitter. The UV emitter may be polychromatic or monochromatic. The emission range of the emitter is preferably located in the absorption range of the photoinitiator and / or photosensitizer.

[0115] In the production of the release coating, the surface is preferably the surface of a carrier, preferably a sheet-like carrier. The composition of the present invention may here be applied on one or both sides of the sheet-like carrier. The sheet-like carrier is preferably selected from the group consisting of paper, cloth, metal foil, and polymer film. The carrier may be smooth or may be provided with a surface structure. Particularly preferred carriers are polypropylene film and polyethylene film.

[0116] The release coating is applied, for example, to adhesive tapes, labels, packaging for self-adhesive hygiene products, food packaging, self-adhesive thermal paper, or liners for bitumen roofing membranes. The release coating has a good release effect on the adhesive materials used in these applications.

[0117] The release effect on an adhesive material, usually an adhesive tape or label in industrial applications, is represented by the release force, and a low release force explains a good release effect. The release force is th determined under the name FTM 10 in accordance with FINAT Handbook 8, Edition, The Hague / NL, 2009, with the modification that storage is carried out under a pressure of 40 °C. The release force depends on the quality of the release coating (e.g., coating uniformity, thickness and / or smoothness), the adhesive material or adhesive, and the test conditions. Therefore, for the evaluation of the release coating, the existing adhesive or adhesive material and the test conditions should be the same. The release force is confirmed using the adhesive tape TESA® 7475, a trademark of Tesa SE (Hamburg, Germany), with a width of 2.5 cm.

[0118] The release coating of the present invention preferably has a release force of at most 20 cN / 2.5 cm, more preferably at most 10 cN / 2.5 cm, and very preferably at most 8 cN / 2.5 cm, and the release force is at least 0.5 cN / 2.5 cm, preferably at least 1 cN / 2.5 cm.

[0119] Without further elaboration, it is believed that those skilled in the art can make the best use of the above description. Therefore, the preferred embodiments and examples should be construed only as descriptive disclosures that are in no way limiting.

[0120] All definitions, embodiments, and descriptions applicable to one aspect of the present invention are applicable to other aspects of the present invention with the necessary modifications, and vice versa.

[0121] The subject matter of the present invention will be described in more detail with reference to FIG. 1 without intending that the subject matter of the present invention be limited thereto.

Brief Description of the Drawings

[0122]

Figure 1

[0123] Examples The following examples are only useful for those skilled in the art to clarify the present invention and do not constitute any limitation of the claimed subject matter.

[0124] Method Epoxide value: The epoxide value was determined in %(weight) according to DIN EN ISO 3001 (1999-11) and ASTM D 1652 (2011).

[0125] Viscosity: Viscosity was measured at 25 °C using a Brookfield R / S-CPS Plus rheometer with an RP75 measuring plate. The test method is described in DIN 53019 (DIN 53019-1 (2008-09), DIN 53019-2 (2001-02) and DIN 53019-3 (2008-09)).

[0126] Acid value: The acid value was determined by titration in mg KOH / polymer g according to DIN EN ISO 2114 (2002-06).

[0127] Hydroxyl value (OH value): The OH value was determined by titration in mg KOH / polymer g according to DIN EN ISO 4629-2 (2016-12).

[0128] Isocyanate value (NCO value): The NCO value was determined by titration in % (by weight) according to DIN EN 1242 (2013-05).

[0129] Gel Permeation Chromatography (GPC): The GPC measurement of the weight average molecular weight M w and the number average molecular weight M n was carried out under the following measurement conditions: column combination SDV 1000 / 10 000 Å (length 55 cm), temperature 35 °C, THF as mobile phase, flow rate 0.35 ml / min, sample concentration 10 g / l, RI detector, evaluation of the polymer against polystyrene standards (162 - 2 520 000 g / mol).

[0130] Material VESTANAT® AT EP-DC 1241: VESTANAT® AT EP-DC 1241 (Evonik Industries AG) is a commercially available adduct of 2-hydroxyethyl propenoate (2-hydroxyethyl acrylate, HEA) and 5-isocyanato-(isocyanatomethyl)-1,3,3-trimethylcyclohexane (isophorone diisocyanate, IPDI) and contains the following isomers: [Chemical formula]

[0131] Constituent (a) - silicone urethane (meth) acrylate according to formula (F) Synthesis S1) Preparation of silicone urethane acrylate according to formula (F) (where m1 = 0, m2 = 2, m3 = 0, d1 = 28, d2 = t = q = 0, x1 = 3, (x2 = 1 and x3 = 0) or (x2 = 1 and x3 = 0), R = CH3, R 1 = H, R 2 = formula (H), R 3 = formula (I), R 4 = H, and R 5 = formula (J))

[0132] Into a 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, while stirring, charge 94.4 g of acrylic acid, 0.3 g of methylhydroquinone, 69.5 g of n-butanol, 41.7 g of methyl isobutyl ketone and 3 g of a 50% aqueous solution of chromium(III) acetate. To this, while heating to 115 °C, add 1291 g of polydimethylsiloxane modified with terminal epoxy groups and having an epoxide oxygen number of 1.32% (by weight). Stirring is continued at 115 - 120 °C until the conversion rate of the epoxy groups determined by the acid value is > 99%. Then, all volatile substances are distilled off at 120 °C and complete vacuum. By filtration, a liquid silicone acrylate having a viscosity at 25 °C of < 200 mPa·s and a hydroxyl value of 52 mg KOH / g is obtained.

[0133] In a 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser, and an internal thermometer, 1078.8 g of the silicone acrylate thus prepared was mixed with 356.2 g of VESTANAT® EP-DC 1241 and 2.87 g of TIB KAT 716 LA, and stirred at 60 °C for 6 hours. The high-viscosity silicone urethane acrylate has a residual NCO content of <0.03% and a number-average molecular weight M n determined by GPC of 4395 g / mol and a weight-average molecular weight M w of 6513 g / mol.

[0134] S2) Preparation of silicone urethane acrylate according to formula (F) (where m1 = 0, m2 = 1, m3 = 1, d1 = 28, d2 = t = q = 0, x1 = 3, (x2 = 1 and x3 = 0) or (x2 = 1 and x3 = 0), R = CH3, R 1 = H, R 2 = formula (H), R 3 = formula (I), R 4 = H, R 5 = formula (J), and R A = formula (K) or (L))

[0135] In a 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser, and an internal thermometer, 253 g of the silicone acrylate having a hydroxyl value of 51 mg KOH / g prepared according to Example S1 was mixed with 40.96 g of VESTANAT® EP-DC 1241 and 0.59 g of TIB KAT 716 LA, and stirred at 60 °C for 6 hours. The resulting silicone urethane acrylate has a viscosity at 25 °C of 1837 mPa·s and a number-average molecular weight M n determined by GPC of 2872 g / mol and a weight-average molecular weight M w of 5377 g / mol.

[0136] S3) Preparation of silicone urethane acrylate according to formula (F) (where m1 = 0, m2 = 2, m3 = 0, d1 = 48, d2 = d3 = t = q = 0, x1 = 3, (x2 = 1 and x3 = 0) or (x2 = 1 and x3 = 0), R = CH3, R1 =H, R 2 =Formula (H), R 3 =Formula (I), R 4 =H, and R 5 =Formula (J))

[0137] Into a 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, while stirring, charge 131.69 g of acrylic acid, 0.6 g of methylhydroquinone, 86.9 g of n-butanol, 3.6 g of 2-(((3-(octyloxy)propyl)imino)methyl)phenol prepared according to EP 3168273 A1 and 1.7 g of a 50% aqueous solution of chromium(III) acetate. To this, while heating to 115 °C, add 2763.5 g of polydimethylsiloxane modified with terminal epoxy groups and having an epoxide oxygen value of 0.92% (by weight). Stir at 115 - 120 °C until the conversion rate of the epoxy groups determined by the acid value is >99%. Then, distill off all volatile substances at 120 °C and 3 mbar under a slight air bleed. By filtration, a liquid silicone acrylate having a hydroxyl value of 30 mg KOH / g is obtained.

[0138] In a 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, mix 3140.8 g of the silicone acrylate prepared in this way with 1123.5 g of acetone, 604.2 g of VESTANAT® EP-DC 1241 and 7.5 g of TIB KAT 716 LA and stir at 60 °C for 6 hours. By distillation at 60 °C and 3 mbar using a slight air bleed, a greenish-brown transparent product having a viscosity of 18216 mPa·s at 25 °C is obtained.

[0139] S4) Preparation of silicone urethane acrylate according to formula (F) (wherein m1 = 0, m2 = 2, m3 = 0, d1 = 8, d2 = d3 = t = q = 0, x1 = 3, x3 = 1, R = CH3, R 1 =C2H5, R 2 =R 3 =Formula (I), R 4 =H, and R 5 =Formula (J))

[0140] Into a 5 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 47.7 g of a hydroxyl-functional siloxane having a hydroxyl value of 200 mg KOH / g prepared according to Example 1 of EP 0940422 B and 57.7 g of Vestanat® EP-DC 1241 are charged, and the mixture is heated to 80 °C with stirring. 0.21 g of TIB® KAT 716 LA is added thereto, and the mixture is stirred at 80 °C for 5 hours. The viscosity increases rapidly during this time. Thereby, a transparent yellow polymer having a high viscosity at 80 °C and solidifying into a glassy mass at room temperature is obtained.

[0141] S5) Preparation of silicone urethane acrylate according to formula (F) (wherein m1 = 0, m2 = 2, m3 = 0, d1 = 78, d2 = d3 = t = q = 0, x1 = 3, x3 = 1, R = CH3, R 1 = C2H5, R 2 = R 3 = formula (I), R 4 = H, and R 5 = formula (J))

[0142] In a 5 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 1055.21 g of a hydroxyl-functional siloxane having a hydroxyl value of 42 mg KOH / g prepared according to the prior art disclosed in EP 0940422 B1 and 281.41 g of Vestanat® EP-DC 1241 are dissolved in 2004.94 g of toluene, and 2.67 g of TIB® KAT 716 LA is added.

[0143] The reaction mixture is heated to 60 °C and stirred for 4 hours. After distilling off toluene at 70 °C, when the target pressure of 20 mbar is reached after 2 hours, a polymer having a very high viscosity at 70 °C and solidifying into a glassy mass at room temperature is obtained. The number average molecular weight M n determined by GPC is 8638 g / mol, and the weight average molecular weight M w is 28 731 g / mol.

[0144] S6) Preparation of silicone urethane acrylate according to formula (F) (where m1 = 0, m2 = 2, m3 = 0, d1 = 48, d2 = d3 = t = q = 0, x1 = 3, x3 = 0, R = CH3, R 1 = R 2 = H, R 3 = formula (I), R 4 = H, and R 5 = formula (J))

[0145] Charge 179.0 g of polydimethylsiloxane modified with a terminal hydroxy group and having a hydroxyl value of 47 mg KOH / g into a 0.5 L four-necked flask equipped with a mechanical stirrer, a reflux condenser, and an internal thermometer. Add 53.3 g of Vestanat® EP DC 1241 and 116.1 g of toluene while stirring. To this, add 0.23 g of TIB® KAT 716 LA. Heat the reaction mixture to 60 °C and stir at 60 °C for 4 hours. Then, distill off the solvent with a rotary evaporator at 80 °C and 2 mbar for 1 hour. A very viscous polymer that solidifies at room temperature is obtained.

[0146] S7) Preparation of silicone urethane acrylate according to formula (F) (where m1 = 1, m2 = 1, m3 = 0, d1 = 28, d2 = d3 = t = q = 0, x1 = 3, (x2 = 1 and x3 = 0) or (x2 = 1 and x3 = 0), R = CH3, R 1 = H, R 2 = formula (H), R 3 = formula (I), R 4 = H, and R 5 = formula (J))

[0147] Into a 0.5 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, while stirring, charge 12.4 g of acrylic acid, 0.032 g of methylhydroquinone, 9.5 g of n-butanol, 0.38 g of 2-(((3-(octyloxy)propyl)imino)methyl)phenol prepared according to EP 3168273 A1 and 0.19 g of a 50% aqueous solution of chromium(III) acetate. To this, while heating to 120 °C, add 303.7 g of a linear polydimethylsiloxane modified with one terminal epoxy group and one terminal trimethylsiloxy group and having an epoxide oxygen value of 0.79% (by weight). Stir at 115 - 120 °C until the conversion rate of the epoxy groups determined by the acid value is >99%. Then distill off all volatile substances at 120 °C and 3 mbar under a slight air bleed. By filtration, a liquid silicone acrylate having a hydroxyl value of 27 mg KOH / g is obtained.

[0148] In a 0.5 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, mix 200.6 g of the silicone acrylate thus prepared with 70.3 g of acetone, 33.8 g of VESTANAT® EP-DC 1241 and 0.23 g of TIB KAT 716 LA and stir at 60 °C for 4 hours. By distillation at 60 °C and 1 - 2 mbar under a slight air bleed, a greenish transparent product having a viscosity of 857 mPa·s at 25 °C is obtained.

[0149] S8) Preparation of silicone urethane acrylate according to formula (F) (wherein m1 = 2, m2 = 0, m3 = 0, d1 = 65, d2 = 4, d3 = t = q = 0, x1 = 3, (x2 = 1 and x3 = 0) or (x2 = 1 and x3 = 0), R = CH3, R 1 = H, R 2 = formula (H), R 3 = formula (I), R 4 = H, and R 5 = formula (J))

[0150] Into a 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, while stirring, charge 37.29 g of acrylic acid, 0.073 g of methylhydroquinone, 21.13 g of n-butanol, 0.887 g of 2-(((3-(octyloxy)propyl)imino)methyl)phenol prepared according to EP 3168273 A1 and 0.422 g of a 50% aqueous solution of chromium(III) acetate. To this, while heating to 115 °C, add 666.64 g of a statistically distributed [polydimethyl(methyl-, glycidoxypropyl)]siloxane copolymer having an epoxy oxygen value of 1.08% (by weight) and a viscosity at 25 °C of 145 mPa·s. Continue stirring at 115 - 120 °C until the conversion rate of the epoxy groups determined by the acid value is >99%. Then, distill off all volatile substances at 120 °C and 3 mbar under a slight air bleed. By filtration, a liquid silicone acrylate having a hydroxyl value of 33.8 mg KOH / g is obtained.

[0151] In a 1 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, mix 215.8 g of the silicone acrylate thus prepared with 77.9 g of acetone, 43.9 g of VESTANAT® EP-DC 1241 and 0.25 g of TIB KAT 716 LA and stir at 60 °C for 4 hours. By distillation at 60 °C and 3 mbar using a slight air bleed, a brown transparent product having a viscosity of 20004 mPa·s at 25 °C is obtained.

[0152] S9) Preparation of silicone urethane acrylate according to formula (F) (wherein m1 = 2, m2 = 0, m3 = 0, d1 = 89, d2 = 6, d3 = 0, t = q = 0, x1 = 3, (x2 = 1 and x3 = 0) or (x2 = 1 and x3 = 0), R = CH3, R 1 = H, R 2 = formula (H), R 3 = formula (I), R 4 = H, and R 5 = formula (J))

[0153] Into a 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, while stirring, charge 167.5 g of acrylic acid, 0.27 g of methylhydroquinone, 79.7 g of n-butanol, 3.35 g of 2-(((3-(octyloxy)propyl)imino)methyl)phenol prepared according to EP 3168273 A1 and 1.60 g of a 50% aqueous solution of chromium(III) acetate. To this, while heating to 115 °C, add 2478.3 g of a statistically distributed [polydimethyl(methyl-, glycidoxypropyl)]siloxane copolymer having an epoxy oxygen value of 1.39% (by weight). Stirring is continued at 115 - 120 °C until the conversion rate of the epoxy groups determined by the acid value is > 97%. Then, all volatile substances are distilled off at 120 °C and 1 mbar of vacuum using a small amount of air bleed. By filtration, a liquid silicone acrylate having a hydroxyl value of 47 mg KOH / g and a viscosity of 760 mPa·s at 25 °C is obtained.

[0154] In a 1 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, mix 2124.8 g of the prepared silicone acrylate with 825 g of acetone, 625.1 g of VESTANAT® EP-DC 1241, 0.28 g of methylhydroquinone and 5.5 g of TIB KAT 716 LA, and stir at 60 °C for 6 hours. By distillation at 60 °C and 1 mbar using a small amount of air bleed, a brown transparent product having a viscosity of 528 Pa·s at 25 °C is obtained.

[0155] The silicone urethane (meth)acrylates are listed in Table 1. The silicone urethane (meth)acrylates according to the present invention have a lower viscosity than the silicone urethane (meth)acrylates not according to the present invention.

[0156]

Table 1-1

[0157]

Table 1-2

[0158] Component (b) - Organic (meth)acrylate (reactive diluent) The organic (meth)acrylates used as component (b) are listed in Table 2.

[0159]

Table 2

[0160] Component (c) - A silicone (meth)acrylate having no urethane group Component (c1): A silicone (meth)acrylate represented by formula (Q) The silicone (meth)acrylates S10, S12 and S13 represented by formula (Q) are prepared according to the prior art methods as described, for example, in EP 0940422 A1. The silicone (meth)acrylates represented by formula (Q) are listed in Table 3.

[0161]

Table 3

[0162] Component (c2): A silicone (meth)acrylate represented by formula (S) The silicone (meth)acrylate represented by formula (S) is prepared according to the prior art methods as disclosed, for example, in EP 3168273 A1 or WO 2017187030 A1. The silicone (meth)acrylates represented by formula (S) are listed in Table 4.

[0163]

Table 4

[0164] Release coating Preparation of the release coating: The performance test of Synthesis Example S1 of the present invention is carried out in a formulation for a release coating. Release coatings are known from the prior art, especially in the form of non-stick coatings on sheet-like carriers, especially for use in adhesive tapes or label laminates therein.

[0165] The formulation for the release coating is prepared in each case by vigorously mixing 78 g of silicone urethane acrylate from Synthesis Example S1, 20 g of hexanediol diacrylate and 2 g of the photoinitiator TEGO® A18 (Evonik Industries AG, Germany).

[0166] The coating composition thus prepared is applied to a sheet-like carrier. This consists of a 50 cm wide biaxially oriented polypropylene film (BoPP), which is corona pre-treated in each case with a generator output of 1 kW before applying the coating composition. The coating composition has a coating weight of approximately 1 g / m 2 and is applied using a 5-roll coating unit from COATEMA® (Coating Machinery GmbH, Dormagen, Germany), and cured by exposure to UV light from a medium-pressure mercury vapor lamp from IST® Metz GmbH (Nurtingen, Germany) at 60 W / cm and a belt speed of 100 m / min in a nitrogen atmosphere with a residual oxygen content of less than 50 ppm.

[0167] The test pieces thus coated are subjected to tests for rubbing, peel force, residual adhesiveness, and abrasion resistance.

[0168] Peeling force: In industrial applications, the peel effect for adhesive materials, which are usually in the form of adhesive tapes or labels, is represented by the peel force (RF), and a low peel force indicates a good peel effect. The peel force depends on the quality of the release coating, the adhesive itself, and the test conditions. Therefore, in the evaluation of the release coating, the same adhesive and the same test conditions need to be used. To determine the peel force, the adhesive tape or label laminate is cut into a width of 2.5 cm and then the adhesive surface is applied to the silicone coating under test in each case. This test is carried out according to the test protocol FTM 10 of the FINAT Handbook, 8th Edition, The Hague / NL, 2009, with storage modified under pressure at 40 °C. The adhesive tape used is tesa® 7475 (a trademark of Tesa SE, Hamburg, Germany). The reported value is the average value from five measurements and is reported in units of cN / 2.5 cm. The results are shown in Table 5.

[0169] Residual Adhesion Force: The residual adhesion force (RAF) is determined according to the test protocol FTM 11 of the FINAT Handbook 8th Edition, The Hague / NL, 2009, except that the storage of the test adhesive strip in silicone contact is 1 minute and the standard surface is an untreated BoPP surface. The adhesive tape used is tesa® 7475 (a trademark of Tesa SE, Hamburg, Germany). The residual adhesion force is a measure of the crosslinking of silicone. When non-polymerized and thus mobile silicone components are present, the residual adhesion force value decreases as the proportion of such components increases. The results are shown in Table 5.

[0170] Abrasion Resistance: The abrasion resistance is determined by an electronic Crockmeter M238BB with an adjusted test setup for the release coating. The coated BoPP substrate is 2A 6 cm × 6 cm black cardboard with a basis weight of and an output of 9 N was stroked at a speed of 60 strokes per minute. The scratched film substrate was evaluated by classifying it in the range of 1 to 10, where 1 has very low abrasion resistance, 10 is very good, and no scratches or wear are visible. The results are shown in Table 5.

[0171]

Table 5

[0172] Table 5 shows formulations with a fixed silicone urethane acrylate and reactive diluent (HDDA) ratio while varying the content of pure silicone acrylate. As can be seen, in a specific window of silicone acrylate (up to about 16%) concentration, the peel force decreases while the abrasion resistance increases, which is surprising and highly desirable. When the silicone acrylate content is further increased to 33% of the formulation, the peel force further decreases, but here the wear decreases, which is less desirable.

Claims

1. The following components: (a) At least one silicone urethane (meth)acrylate having the following: - At least three (meth)acrylate groups, and - Urethane groups that are not more numerous than (meth)acrylate groups; (b) At least one organic (meth)acrylate that does not contain a silicon atom; (c) at least one silicone (meth)acrylate that does not have a urethane group; (d) at least one curing catalyst, if applicable; (e) at least one additive, depending on the circumstances; (f) at least one solvent, depending on the case; A composition comprising or consisting thereof - 20-70% (by weight) of component (a); - 20-80% (by weight) of component (b); - At least 1-60% (by weight) of component (c); - 0-5% (by weight) of component (d); - 0-20% (by weight) of component (e); - 0-10% (by weight) of component (f); However, it is contained based on the total weight of the components (a) to (f) and / or the total weight of the composition. A composition characterized by the following features.

2. The silicone urethane (meth)acrylate has m (meth)acrylate groups and n urethane groups, During the ceremony, m is an integer of at least 3; n is an integer of at least 2; However, m ≥ n, The composition according to claim 1, characterized in that...

3. The aforementioned silicone urethane (meth)acrylate is represented by formula (B), X (-Y) ｐ Formula (B) During the ceremony, X is a p-valent silicone radical; Y is bonded to the silicon atom of the silicon radical, In each case, independently selected from the group consisting of monovalent organic radicals having at least one urethane group and at least one (meth)acrylate group; p is an integer of at least 1. The composition according to claim 1, characterized in that...

4. The silicone urethane (meth)acrylate contains a unit represented by formula (C), [R ａ Y ｂ SiO （４－ａ－ｂ）／２ formula (C) During the ceremony, a is an integer between 0 and 2; b is an integer between 1 and 3; However, a + b is between 1 and 3; In each case, R is independently selected from the group consisting of monovalent organic radicals that do not have a urethane group; Y is as defined in claim 3, The composition according to claim 3, characterized in that...

5. The silicone urethane (meth)acrylate contains the group of formula (A), 【Chemistry 1】 During the ceremony, Z １ In each case, independently, -CH ３ Selected from the group consisting of and -H; Z ２ It is an alkylene radical derived from a divalent organic radical; Z ３ is an organic radical with a (q+1) valency, where q is an integer organic radical between 1 and 3; Z ４ is, in each case, independently selected from the group consisting of -CH ３ and -H; In the equation, each dotted line represents a covalent bond. The composition according to claim 1, characterized in that...

6. The aforementioned silicone urethane (meth)acrylate is represented by formula (F), M ｍ１ M ＵＡ ｍ２ M Ａ ｍ３ D ｄ１ D ＵＡ ｄ２ D Ａ ｄ３ T ｔ Q ｑ Formula (F), During the ceremony, M=[R ３ SiO １／２ ]; M ＵＡ =[R ２ (R ＵＡ )SiO １／２ ]; M Ａ =[R ２ (R Ａ )SiO １／２ ]; D=[R ２ SiO ２／２ ]; D ＵＡ =[R(R ＵＡ )SiO ２／２ ]; D Ａ =[R(R Ａ )SiO ２／２ ]; T=[RSiO ３／２ ]; Q = [SiO ４／２ ] and; m1 is an integer between 0 and 32; m² is an integer between 0 and 32; m3 is an integer between 0 and 32; d1 is an integer between 1 and 1000; d2 is an integer between 0 and 10; d3 is an integer between 0 and 10; t is an integer between 0 and 10; q is an integer between 0 and 10; however, m1 + m2 + m3 is at least 2; m² + d² is at least 1; In each case, R is independently selected from the group consisting of monovalent organic radicals that do not have a urethane group or a (meth)acrylate group; R ＵＡ In each case, independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group and at least one urethane group; R ２ In each case, independently, hydrogen radicals, R ３ and selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group; R3 is independently selected in each case from the group consisting of monovalent organic radicals having at least one urethane group and at least one (meth)acrylate group; In each case, R A is independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group but no urethane group. The composition according to claim 1, characterized in that...

7. R ＵＡ Or Y is given by formulas (M), (N), (O), and (P): 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 The composition according to claim 3 or 6, characterized by being represented by at least one of the following.

8. At least one silicone (meth)acrylate of component (c) is represented by formula (Q), and / or at least one silicone (meth)acrylate of component (c) is represented by formula (S), M Ａ ｍ１ D ｄ１ Formula (Q); During the ceremony, M Ａ =[R ２ (R Ａ )SiO １／２ ]; D = [R ２ SiO ２／２ ] and; m1 is an integer of 2; d1 is an integer between 1 and 10000; In each case, R is independently selected from the group consisting of monovalent organic radicals that do not have a urethane group or a (meth)acrylate group. ； R Ａ In each case, independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group but no urethane group. M ｍ１ D ｄ１ D Ａ ｄ２ D ＡＣ ｄ３ Formula (S); During the ceremony, M=[R ３ SiO １／２ ]; D=[R ２ SiO ２／２ ]; D Ａ =[R(R Ａ )SiO ２／２ ]; D ＡＣ = [R(R ＡＣ ) SiO ２／２ ] and; During the ceremony, R, m1, and d1 are as defined for equation (Q); d2 is an integer between 1 and 20; d3 is an integer between 0 and 3; R Ａ In each case, independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group but no urethane group. ; R ＡＣ In each case, independently selected from the group consisting of monovalent organic radicals having at least one carboxylic acid ester group but lacking a (meth)acrylate group and lacking a urethane group, The composition according to claim 1, characterized in that...

9. The composition according to claim 1, characterized in that the composition is curable.

10. The following steps: (i) A step of preparing a mixture of component (a) and component (f); (ii) A step of preparing a mixture by adding at least one of the constituent components (b) to (e) to the mixture of step (i); (iii) A step of removing the component (f) from the mixture of step (iii); (iv) If the constituent components have not been added in step (ii), a step of preparing a mixture by adding at least one of the constituent components (b) to (e) to the mixture in step (iiii), A method for preparing the composition according to claim 1 or 2, comprising or consisting of the following.

11. The following indirect or direct successive processes: a. A step of applying the composition according to claim 1 or 2 to a surface; b. A step of curing the composition. A method for preparing a release coating, protective film, or protective coating, including the following.

12. A release coating, protective film, or protective coating that can be obtained by curing the composition according to claim 1 or 2.

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