Silicone urethane (meth)acrylates, and their use in 3D printing resins and coating compositions

Abstract

The present invention relates to silicone urethane (meth)acrylates, in particular having at least three (meth)acrylate groups and not more urethane groups than (meth)acrylate groups, to a process for preparing said silicone urethane (meth)acrylates, to compositions comprising said silicone urethane (meth)acrylates, and to their use in the production of release coatings, protective films and protective coatings, and in the manufacture of 3D printed objects by stereolithography.

Description

[Technical Field]

[0001] The present invention relates to a silicone urethane (meth)acrylate particularly having at least three (meth)acrylate groups and no more than three urethane groups than (meth)acrylate groups, a method for preparing the silicone urethane (meth)acrylate, a composition comprising the silicone urethane (meth)acrylate, and their use in the production of release coatings, protective films, and protective coatings, as well as their use in the manufacture of 3D printed objects by stereolithography.

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

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

[0004] Chinese Patent Application Publication No. 106519182 discloses a silicone urethane acrylate for use in the field of peel-off coatings. The silicone urethane acrylate is, (1) A step of reacting organosilicon glycol and diisocyanate in a ratio of 1:2 between hydroxyl groups and isocyanate groups. (2) A step in which hydroxyethyl acrylate or hydroxyethyl methacrylate is reacted with the prepolymer obtained in step (1) in a ratio of 1:1 between hydroxyl groups and isocyanate groups. It is prepared by a method that includes [a specific method].

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

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

[0007] However, silicone urethane (meth)acrylates known in the art typically exhibit only moderate photocuring rates, high viscosity, or are even solid at room temperature, thereby making them difficult to process. To improve their processability, processing of silicone urethane (meth)acrylates may be carried out at higher temperatures or by adding larger amounts of solvent or reactive diluents, which can result in other drawbacks such as increased energy consumption, additional method steps for solvent removal, and / or potential adverse effects on the desired properties of the cured product. To facilitate processing, a higher curing rate and increased curing depth are also preferable. Furthermore, it is preferable that the cured product is flexible and possesses good mechanical properties such as high elongation at break. It is also preferable that the cured product is an elastomer material, i.e., that 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. It is also necessary to avoid highly toxic or hazardous compounds in the synthesis of silicone urethane (meth)acrylates.

[0008] Therefore, there is still a need to provide a silicone urethane (meth)acrylate that has advantages over the prior art. Consequently, the problem addressed by the present invention was to overcome at least one drawback of the prior art.

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

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

[0011] According to a first aspect of the present invention, - At least three (meth)acrylate groups, - Not more than (meth)acrylate groups, preferably exactly the same number of urethane groups as (meth)acrylate groups A silicone urethane (meth)acrylate having the properties of is provided.

[0012] According to a second aspect of the present invention, formula (A): [ka] It includes the base of, During the ceremony, Z 1 However, in either case, it is independently selected from the group consisting of CH3 or H, and is preferably H. Z 2 However, a divalent organic radical, preferably an alkylene radical, preferably OCN-Z 2 - An alkylene radical derived from isophorone diisocyanate as the diisocyanate of CNO, Z 3 However, it is a (q+1) valent organic radical, where q is an integer organic radical from 1 to 3, preferably an alkylene radical, preferably -(C2H4)-. Z 4 However, in either case, it is independently selected from the group consisting of -CH3 and -H, and is preferably H. In the equation, each dotted line represents a covalent bond. A silicone urethane (meth)acrylate, preferably a silicone urethane (meth)acrylate according to a first aspect of the present invention, is provided.

[0013] A third aspect of the present invention provides a method for preparing the silicone urethane (meth)acrylate, wherein the silicone urethane (meth)acrylate is formed by a reaction between at least one hydroxy-functional silicone (meth)acrylate and at least one isocyanate-functional urethane (meth)acrylate.

[0014] According to a fourth aspect of the present invention, the following components: (a) At least one silicone urethane (meth)acrylate according to the present invention, (b) Optionally, at least one organic (meth)acrylate that does not contain any silicon atoms, (c) Optionally, at least one silicone (meth)acrylate that does not have any urethane groups, (d) Optionally, at least one curing catalyst, (e) Optionally, at least one additive, (f) Optionally, at least one solvent A composition containing or comprising these is provided.

[0015] According to a fifth aspect of the present invention, a method for preparing the composition, (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 components (b) to (e), preferably component (b) and / or (c), to the mixture of step (i). (iii) A step of (essentially) removing component (f) from the mixture of step (ii), (iv) A step of preparing a mixture by optionally adding at least one of components (b) to (e) to the mixture of step (iii) if the component was not added in step (ii). A method including this is provided.

[0016] According to a fifth aspect of the present invention, a release coating, protective film, or protective coating that can be obtained by curing the composition, or a 3D printed object that can be obtained by 3D printing the composition, is provided.

[0017] As used herein, the singular forms "a," "an," and "the" refer to multiple objects unless otherwise clearly indicated by the context.

[0018] As used herein, the terms “comprising” and “comprises” are synonymous with “including,” “includes,” “containing,” or “contains,” and are inclusive or non-exclusive, not excluding additional unlisted components, elements, or method steps.

[0019] When quantities, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper limits, lower limits, or preferred upper and lower limits, it should be understood that any range obtainable by combining any upper or preferred value with any lower or preferred value is also specifically disclosed, regardless of whether the obtained range is explicitly mentioned in the context.

[0020] From this point forward, numerical ranges are reported in the format "X~Y," where X and Y represent the limits of the range. Unless otherwise specified, this is equivalent to the statement "at least from X to Y (including Y)." Therefore, unless otherwise specified, range descriptions include the range limits X and Y.

[0021] In this specification, the terms “preferred” and “preferred” are frequently used to refer to embodiments of the disclosure that may provide a particular benefit under certain circumstances. However, the enumeration of one or more preferred embodiments is not intended to imply that other embodiments are not useful, nor is it intended to exclude these other embodiments from the scope of the disclosure.

[0022] Where measurements, parameters, or material properties determined by measurement are reported below, these are measurements, parameters, or material properties taken at 25°C and preferably at a pressure of 101325 Pa (standard pressure), unless otherwise specified.

[0023] When used herein, room temperature (RT) is 23°C ± 2°C.

[0024] The expression "(meth)acryl" represents "methacryl" and / or "acryl". Thus, the expression "(meth)acrylate" represents "methacrylate" and / or "acrylate". As used herein, "acrylate" refers to "acrylic acid ester", and "methacrylate" refers to "methacrylic acid ester".

[0025] In the context of this invention, silicone urethane (meth)acrylate is understood to mean an organic siloxane that contains urethane groups and has methacrylate groups and / or acrylate groups, hereinafter also referred to as (meth)acrylic acid ester groups. The organic siloxane is hereinafter also simply referred to as siloxane.

[0026] The organic siloxane has an organic radical bonded to a silicon atom and a structural unit of the formula:

Chemical formula

Chemical formula

[0027] The various repeating units in the following equations (C), (F), (Q), and (S) can be statistical distributions. These statistical distributions may have a block-by-block structure with any number of blocks and any sequence, or they may be random distributions, which may have alternating structures, or, if chains exist, may form gradients along them, and in particular, they may also form any mixed form thereof, in which groups of different distributions may follow one another at will. Specific embodiments can be defined below in such a way that features such as indices, or structural components, or ranges, or statistical distributions are subject to the limitations of the embodiment. All other features not affected by the limitations remain unchanged.

[0028] If a molecule / molecular fragment has one or more stereocenters (stereogenic centers), or can be distinguished into isomers based on symmetry, or can be distinguished into isomers based on other effects, such as restricted rotation, then all possible isomers are included by the present invention.

[0029] In this document, unless otherwise specified, the molecular weight given is the number-average molecular weight (M). n) refers to the values ​​obtained by gel permeation chromatography (GPC), as shown in the example.

[0030] When a document is referenced within the context of this specification, its entirety is intended to be part of the disclosure of the present invention.

[0031] In a first aspect of the present invention, - At least three (meth)acrylate groups, - Not more than (meth)acrylate groups, preferably exactly the same number of urethane groups as (meth)acrylate groups A silicone urethane (meth)acrylate having the properties of is provided.

[0032] The silicone urethane (meth)acrylate preferably has m (meth)acrylate groups and n urethane groups. m is an integer of at least 3, preferably 3 to 5, and more preferably 4. n is an integer of at least 2, preferably 2 to 4, and more preferably 4. However, m ≥ n, preferably m = n.

[0033] Possible combinations (m;n) of m (meth)acrylate groups and n urethane groups include (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).

[0034] Silicone urethane (meth)acrylate is given by formula (B): X(-Y) p Formula (B) Represented by, During the ceremony, X is a p-valent silicone radical, Y is bonded to the silicon atom of the silicon radical, In either case, a monovalent organic radical having at least one urethane group and at least one (meth)acrylate group is independently selected from the group, Preferably, in either case, the monovalent organic radicals having two (meth)acrylate groups and one or two urethane groups are independently selected from the group, More preferably, in either case, independently 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, and more preferably 2. It is preferable.

[0035] Silicone radicals can be linear, branched, cyclic, or a combination thereof. A linear silicone radical is preferred. A divalent polydimethylsiloxane radical is particularly preferred.

[0036] Silicone urethane (meth)acrylate is used in formula (C): [R a Y b SiO (4-a-b) / 2 ] Formula (C) Includes units represented by During the ceremony, a is an integer between 0 and 2, preferably 1 or 2. b is an integer between 1 and 3, preferably 1. However, a+b is between 1 and 3. In all cases, R is independently selected from the group consisting of monovalent organic radicals that do not contain any urethane groups. Preferably, in either 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. It is preferable.

[0037] Preferably, the silicone urethane (meth)acrylate has exactly two units represented by formula (C) as defined above, and each of these units has two radicals R and one radical Y, i.e., a=2 and b=1 is particularly preferred.

[0038] In a further aspect of the present invention, preferably, a silicone urethane (meth)acrylate according to the first aspect of the present invention, and more preferably, a radical Y containing formula (A): [ka] It includes the base of, During the ceremony, Z 1 However, in either case, it is independently selected from the group consisting of CH3 or H, and is preferably H. Z 2 However, a divalent organic radical, preferably an alkylene radical, preferably OCN-Z 2 - An alkylene radical derived from isophorone diisocyanate as the diisocyanate of CNO, Z 3 However, it is a (q+1) valent organic radical, where q is an integer organic radical from 1 to 3, preferably an alkylene radical, preferably -(C2H4)-. Z 4 However, in either case, it is independently selected from the group consisting of -CH3 and -H, and is preferably H. In the equation, each dotted line represents a covalent bond. Silicone urethane (meth)acrylate is provided.

[0039] Examples of covalent bonds represented by dotted lines are bonds to hydrogen radicals or to organic radicals such as alkyl or alkylene radicals, which can be linear, branched, or cyclic and can be optionally interrupted by oxygen atoms. Preferably, at least one of the dotted lines represents a covalent bond to an organic radical that itself has a covalent bond to a silicon atom, and the organic radical is preferably a divalent hydrocarbon radical that can be interrupted by an oxygen atom.

[0040] Z 2 However, in any case, it is preferable to independently select from the group of divalent, saturated or unsaturated, linear or branched or cyclic hydrocarbon radicals having 1 to 30 carbon atoms. 2 The formula is OCN-Z 2 -CNO (formula (D)) may be a residue of a diisocyanate. The term "diisocyanate residue" 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 However, the formula OCN-Z 2 -A divalent radical derived from the diisocyanate of CNO, wherein the diisocyanate is particularly preferably IPDI.

[0041] Z 3 However, in any case, it is preferable to independently select from the group of (q+1) valence, saturated or unsaturated, linear or branched or cyclic hydrocarbon radicals having 2 to 30 carbon atoms. 3 Equation (E): [ka] It can be a residue of a hydroxy-functional (meth)acrylate.

[0042] Examples of suitable hydroxy-functional (meth)acrylates are shown below. Hydroxyethyl acrylate is particularly preferred.

[0043] Silicone urethane (meth)acrylate is given 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) Represented by, During the ceremony, 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 ], m1 is an integer between 0 and 32, preferably between 0 and 22, more preferably 0. m2 is an integer between 0 and 32, preferably between 1 and 10, more preferably between 2. m3 is an integer between 0 and 32, preferably between 0 and 22, more preferably 0. d1 is an integer between 1 and 1000, preferably between 5 and 500, more preferably between 10 and 400. d2 is an integer between 0 and 10, preferably between 0 and 5, more preferably 0. d3 is an integer between 0 and 10, preferably between 0 and 5, more preferably 0. t is an integer between 0 and 10, preferably between 0 and 5, more preferably between 1 and 5. q is an integer between 0 and 10, preferably between 0 and 5, more preferably between 1 and 5. however, m1+m2+m3 is at least 2, preferably 2-20, more preferably 2-10. m2+d2 is at least 1, preferably 2-10, more preferably 2-6. During the ceremony, In each case, R is independently selected from the group consisting of monovalent organic radicals that do not have any urethane or (meth)acrylate groups. Preferably, in either case, independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 30 carbon atoms, More preferably, a methyl radical, R UA In either case, it is 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 either case, the monovalent organic radicals having two (meth)acrylate groups and one or two urethane groups are independently selected from the group, More preferably, in either case, formula (G): [ka] Independently selected from the group consisting of monovalent organic radicals represented by, x1 is an integer between 1 and 3, preferably 3. R 1 In either case, these are hydrogen radicals, monovalent hydrocarbon radicals having 1 to 6 carbon atoms, and R 2 , and R 3 Independently selected from the group consisting of, Preferably, in either case, the hydrogen radical and the monovalent hydrocarbon radical having 1 to 6 carbon atoms are independently selected from the group, More preferably, a hydrogen radical, R 2 In either case, hydrogen radicals, R 3 , and independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group, Preferably, in either case, R 3 , and independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group, More preferably, in either case, formula (H): [ka] Independently selected from monovalent radicals, x² = (1 - x³), R 3 In either case, it is independently selected from the group consisting of monovalent organic radicals having at least one urethane group and at least one (meth)acrylate group, Preferably, in either case, the monovalent organic radicals are independently selected from the group consisting of exactly two urethane groups and exactly one (meth)acrylate group, More preferably, in either case, formula (I): [ka] Independently selected from the group consisting of monovalent organic radicals, x3 is an integer selected from 0 or 1, preferably 0. R 4 In either case, it is independently selected from a hydrogen radical or a methyl radical, and is preferably a hydrogen radical. R 5 In each case, these are independently selected from the group of divalent, saturated or unsaturated, linear, branched or cyclic hydrocarbon radicals having 1 to 30 carbon atoms. Preferably, formula (J): [ka] It is a divalent radical, R A In either case, it is independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group but no urethane group, Preferably, in either case, independently selected from the group consisting of monovalent radicals represented by formula (K) or (L), More preferably, in either case, independently selected from the group consisting of monovalent radicals represented by formula (K), [ka] In the formula, x1 and R 4 This is as previously defined. It is preferable.

[0044] Radical R UA Or Y, each of the following equations: (M), (N), (O), and (P): [ka] It is even more preferable that it be represented by [this].

[0045] Preferably, the following applies to the silicone urethane (meth)acrylate according to formula (F): m1=d2=t=q=0, m2=2, d1 is 1 to 1000, preferably 5 to 500, more preferably 10 to 400, and even more preferably 20 to 100.

[0046] It is preferable that the (meth)acrylate group of the silicone urethane (meth)acrylate is an acrylate group.

[0047] Preferably, the silicone urethane (meth)acrylate of the present invention does not contain any groups other than the urethane group that contain the -(C=O)-NH- portion of the formula.

[0048] The silicone urethane (meth)acrylate preferably has a viscosity of less than 200 Pa·s at 25°C, preferably 0.5 to 150 Pa·s, and more preferably 10 to 100 Pa·s. The glass transition temperature is preferably determined as described in the example.

[0049] The silicone urethane (meth)acrylate preferably has a weight-average molecular weight Mw of 1,000 to 20,000 g / mol, preferably 2,000 to 15,000 g / mol, and more preferably 3,000 to 10,000 g / mol. The weight-average molecular weight is preferably determined as described in the examples.

[0050] The silicone urethane (meth)acrylate preferably has a number-average molecular weight Mn of 1000 to 10000 g / mol, more preferably 1500 to 7500 g / mol, and more preferably 2000 to 5000 g / mol. The number-average molecular weight is preferably determined as described in the examples.

[0051] The cured silicone urethane (meth)acrylate has a glass transition temperature (T) of less than 100°C, preferably 20-80°C, more preferably 40-70°C. g It is preferable that it has ). The glass transition temperature is preferably determined by differential scanning calorimetry (DSC) according to the DSC method DIN 53765 at a heating rate of 10 K / min.

[0052] Silicone urethane (meth)acrylate is, (1) A step of reacting at least one hydroxy-functional silicone (meth)acrylate with at least one diisocyanate while forming at least one urethane group to obtain an isocyanate-functional prepolymer. (2) A step in which at least one hydroxy-functional (meth)acrylate is reacted with the isocyanate-functional prepolymer obtained in step (1) while forming at least one urethane bond. It can be prepared by a method including

[0053] Those skilled in the art know how to carry out the reaction and select suitable reaction conditions to achieve a high yield, as described, for example, in Korean Published Patent No. 20170128955 and Chinese Patent Application Publication No. 106519182. For example, it is preferable that the molar ratio of hydroxyl groups to isocyanate groups be about 1:2 in step (1) and about 1:1 in step (2).

[0054] Surprisingly, an alternative method for producing silicone urethane (meth)acrylate is far more preferable. According to this method, a hydroxy-functional silicone (meth)acrylate is reacted with an isocyanate-functional urethane (meth)acrylate. This application of the method allows for a further reduction in viscosity.

[0055] Therefore, a further aspect of the present invention is a method for preparing a silicone urethane (meth)acrylate, wherein the silicone urethane (meth)acrylate is formed by the reaction of at least one hydroxy-functional silicone (meth)acrylate with at least one isocyanate-functional urethane (meth)acrylate.

[0056] The reaction between hydroxy-functional silicone (meth)acrylate and isocyanate-functional urethane (meth)acrylate involves the reaction of a free NCO group with a hydroxyl group and has been frequently described (International Publication No. 2010 / 072439 and the references cited therein). This reaction can occur with or without a solvent. It is generally carried out in a temperature range between 40°C and 80°C. The reaction generally takes 4 to 8 hours. This can be favorably 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 octanoate, and bismuth neodecanoate. Examples of suitable tertiary amines are triethylamine or diazobicyclooctane. A suitable reaction assembly includes all conventional apparatus, such as tanks, static mixers, and extruders, preferably assemblies with mixing or stirring functions. The NCO / OH ratio is typically 2:1 to 1:2, preferably 1.5:1 to 1:1.5, and more preferably 1:1. The reaction may be carried out in the presence of a solvent, preferably in the absence of a solvent. A suitable solvent is, for example, acetone. To avoid polymerization of the (meth)acrylate group, 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 an isocyanate-functional urethane (meth)acrylate that can react with the hydroxyl group of the hydroxyl-functional silicone (meth)acrylate. If a solvent is used, it may preferably be removed after the completion of the reaction, preferably under vacuum, or after the preparation of the composition according to the present invention.

[0057] 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. It is preferable that the hydroxy-functional silicone (meth)acrylate be formed by the reaction of at least one epoxy-functional silicone with (meth)acrylic acid and / or at least one hydroxy-functional (meth)acrylate. It is even more preferable that the hydroxy-functional silicone (meth)acrylate be 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 herein. Examples of suitable hydroxy-functional (meth)acrylates that can be used are the same as those that can be used in the synthesis of isocyanate-functional urethane (meth)acrylates as described below.

[0058] Examples of isocyanate-functionalized 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, for example, as described in International Publication No. 2010 / 072439 and International Publication No. 2010 / 115644. A commercially available isocyanate-functionalized urethane (meth)acrylate that can be used is, for example, VESTANAT® EP DC-1241 (available from Evonik Industries AG, Germany). Isocyanate-functionalized urethane (meth)acrylates can be prepared by reacting a diisocyanate with a hydroxy-functionalized (meth)acrylate while forming a urethane bond, as described in International Publication No. 2010 / 072439.

[0059] Preferred diisocyanates are, for example, Houben-Weyl, Methoden der organischen Chemie, Volume 14 / 2, on pages 61 to 70, and Justus Liebigs, Annalen der Chemie 562, on pages 75 to 136.As described in the paper by Siefken, aliphatic, alicyclic, and aromatic aliphatic (i.e., aryl-substituted aliphatic) diisocyanates, e.g., 1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,9-diisocyanato-5-methylnonane, 1,8-Diisocyanato-2,4-dimethyloctane, 1,12-dodecane diisocyanate, ω,ω'-Diisocyanatodipropyl ether, Cyclobutene 1,3-Diisocyanate, Cyclohexane 1,3-Diisocyanate, Cyclohexane 1,4-Diisocyanate, 3-Isocyanatomethyl-3,5,5-Trimethylcyclohexyl isocyanate (Isophorone diisocyanate, IPDI), 1,4-Diisocyanatomethyl-2,3,5,6-Tetramethylcyclohexane, Decahydro-8-methyl( 1,4-methano-naphthalene)-2,5-Iridimethylene diisocyanate, Decahydro-8-methyl(1,4-methano-naphthalene)-3,5-Iridimethylene diisocyanate, Hexahydro-4,7-methanoindan-1,5-Iridimethylene diisocyanate, Hexahydro-4,7-methanoindan-2,5-Iridimethylene diisocyanate, Hexahydro-4,7-methanoindan-1,6-Iridimethylene diisocyanate, Hexahydro-4,7-methanoindan-2,5-Iridimethylene Methylene diisocyanate, hexahydro-4,7-methanoindan-1,5-irene diisocyanate, hexahydro-4,7-methanoindan-2,5-irene diisocyanate, hexahydro-4,7-methanoindan-1,6-irene diisocyanate, hexahydro-4,7-methanoindan-2,6-irene diisocyanate, 2,4-hexahydrotolylene diisocyanate, 2,6-hexahydrotolylene diisocyanate, 4,4'-methylenedicyclohexyl diisocyanate (4,4'-H. 12 MDI), 2,2'-methylenedicyclohexyl diisocyanate (2,2'-H 12MDI), 2,4-methylenedicyclohexyl diisocyanate (2,4-H 12 MDI), or other mixtures thereof, 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 paper previously mentioned 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 alicyclic diisocyanates, e.g., IPDI, HDI, and H 12 MDI and similar materials, as well as mixtures of their isomers, particularly IPDI, are used. The diisocyanate is an embodiment of the diisocyanate of formula (D) as given earlier.

[0060] Preferred hydroxy-functional (meth)acrylates are all compounds having not only at least one methacrylate or acrylate functional group, but also exactly one hydroxyl group. Further components may be aliphatic, alicyclic, aromatic, or heterocyclic alkyl groups. Oligomers or polymers are also conceivable. For example, 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 hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, and hydroxyhexyl vinyl ether are preferred. Hydroxyethyl acrylate is particularly preferred. It is also possible to use mixtures of two or more of these hydroxy-functional (meth)acrylates. The hydroxy-functional (meth)acrylate is an embodiment of the hydroxy-functional (meth)acrylate of formula (E) as shown above.

[0061] The silicone urethane (meth)acrylate according to the present invention is typically used as an ingredient in compositions for various applications.

[0062] Therefore, a further embodiment of the present invention comprises the following components: (a) At least one silicone urethane (meth)acrylate prepared according to and / or by the method according to the present invention, (b) Optionally, at least one organic (meth)acrylate that does not contain any silicon atoms, (c) Optionally, at least one silicone (meth)acrylate that does not have any urethane groups, (d) Optionally, at least one curing catalyst, (e) Optionally, at least one additive A composition containing or (essentially) consisting of these.

[0063] The composition is based on the total weight of the sum of components (a) to (e) and / or the total weight of the composition, preferably based on the total weight of the composition. - At least component (a) in 5 to 100, preferably 5 to 20, more preferably 10 to 20% by weight, - At least component (b) in 0-60, preferably 0-30, more preferably 5-15% by weight, - At least component (c) in 0-95, preferably 65-85, more preferably 70-80% by weight, - Component (d) in an amount of 0-5, preferably 0.1-3, more preferably 0.5-2.5% by weight, - Component (e) in an amount of 0-20, preferably 0-10, more preferably 0-5% by weight, - Component (f) in an amount of 0-10, preferably 0-5, more preferably 0-1% by weight, Preferably, it includes or consists of (essentially) these.

[0064] One or more silicone urethane (meth)acrylates according to the present invention are also referred to as component (a) in this specification.

[0065] The amount of silicone urethane (meth)acrylate (component (a)) present in the composition of the present invention is preferably 5 to 100% by weight, preferably 5 to 20% by weight, and 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.

[0066] The composition according to the present invention preferably further comprises component (b). Component (b) may be used as a reactive diluent to reduce and adjust the viscosity of the composition. Alternatively, component (b) may be used as a crosslinking agent. Component (b) of the composition consists of one or more organic (meth)acrylates that do not contain any silicon atoms. Therefore, the organic (meth)acrylates are silicon atom-free. It is preferable that the organic (meth)acrylates consist only of the elements carbon, hydrogen, oxygen, and nitrogen. It is also preferable that the organic (meth)acrylates have 2 to 6 (meth)acrylate groups. Such compounds are described in "Radiation Curing: Coatings and Printing Inks", 2008, Vincentz Network, Hanover, Germany, by Patrick Gloeckner et al., in the European Coatings Tech Files.

[0067] Particularly preferred organic (meth)acrylates are disclosed in International Publication Nos. 2016 / 096595 and International Publication Nos. 2018 / 001687. Examples of organic (meth)acrylates may be selected from, but are not limited to, 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.

[0068] Suitable organic (meth)acrylates include 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 (polyethylene glycol 600 diacrylate with Mw 700 g / mol, Allnex SA, Germany), Ebecryl® 45 (Allnex SA, Germany), PETIA (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, Allnex SA, Germany), Ebecryl® 150 (bisphenol A derivative diacrylate, Allnex SA, Ebecryl® 605 (a 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, It is also marketed under the trademark names SR 489 (tridecyl acrylate, Sartomer, France) and SR 489 (tridecyl acrylate, Sartomer, France).

[0069] Suitable organic (meth)acrylates are also commercially available from Evonik Industries AG (Germany) under the VISIOMER® product line. Preferred compounds include 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), methacrylate of aliphatic alcohols having an average of 13.0 carbon atoms (VISIOMER® Terra C13-MA), or methacrylate of fatty alcohols having an average of 17.4 carbon atoms (VISIOMER® Terra This is C17.4-MA).

[0070] The compositions of the present invention more preferably include 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.

[0071] In the organic (meth)acrylate (component (b)), it is preferable that the (meth)acrylate group of the silicone (meth)acrylate is an acrylate group.

[0072] Organic (meth)acrylate (component (b)) It is also preferable that the (meth)acrylate group of the silicone (meth)acrylate is a (meth)acrylate group.

[0073] The amount of organic methacrylate (component (b)) present in the composition of the present invention is preferably 0 to 60% by weight, preferably 0 to 30% by weight, and more preferably 5 to 15% by weight, based on the total weight of the sum of components (a) to (e) and / or based on the total weight of the composition.

[0074] The composition according to the present invention preferably contains component (c). Component (c) consists of at least one silicone (meth)acrylate that does not contain any urethane groups. Therefore, the silicone (meth)acrylate is urethane group-free.

[0075] 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 =[R2(R A )SiO 1 / 2 ], D=[R2SiO 2 / 2 ], m1 is an integer of 2, d1 is an integer between 1 and 10000, preferably between 50 and 5000, more preferably between 70 and 2000. During the ceremony, In each case, R is independently selected from the group consisting of monovalent organic radicals that do not have any urethane or (meth)acrylate groups. Preferably, in either case, independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 30 carbon atoms, More preferably, a methyl radical, R A In either case, it is independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group but no urethane groups, Preferably, in any case, the formula (R):

Chemical formula

[0076] 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). Thus, component (c) consists of component (c1) and / or component (c2), where 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).

[0077] Examples of silicone (meth)acrylate (component (c1)) according to formula (Q) are known to those skilled in the art and can be prepared, for example, as described in European Patent Application Publication No. 0940422.

[0078] Examples of silicone (meth)acrylate (component (c2)) according to formula (S) are also known to those skilled in the art and can be prepared, for example, as described in European Patent Application Publication No. 3168273 and International Publication No. 2017187030.

[0079] The amount of 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, and more preferably 70 to 80% by weight, based on the total weight of the sum of components (a) to (e) and / or based on the total weight of the composition.

[0080] It is particularly preferable that the amount of silicone (meth)acrylate (component (c1)) according to formula (Q) present in the composition of the present invention is 0 to 95% by weight, preferably 65 to 85% by weight, and more preferably 70 to 80% by weight, based on the total weight of the sum of components (a) to (e) and / or based on the total weight of the composition.

[0081] It is particularly preferable that the amount of silicone (meth)acrylate (component (c2)) according to formula (S) present in the composition of the present invention is 0 to 95% by weight, preferably 65 to 85% by weight, and more preferably 70 to 80% by weight, based on the total weight of the sum of components (a) to (e) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0082] It is preferable that the (meth)acrylate group of the silicone (meth)acrylate (component (c1)) represented by general formula (Q) is an acrylate group. Similarly, it is preferable that the (meth)acrylate group of the silicone (meth)acrylate (component (c2)) represented by general formula (S) is an acrylate group. It is more preferable that the (meth)acrylate group of the silicone (meth)acrylate (component (c1)) represented by formula (Q) and the (meth)acrylate group of the silicone (meth)acrylate (component (c1)) represented by formula (S) are acrylate groups.

[0083] It is particularly preferable that the (meth)acrylate groups of components (a), (b), and (c) (such as components (c1) and (c2)) are acrylate groups.

[0084] It is particularly preferable that the (meth)acrylate groups of components (a) and (c) (such as (c1) and (c2)) are acrylate groups, and the (meth)acrylate group of component (b) is a (meth)acrylate group.

[0085] Component (d) of the composition according to the present invention comprises 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 chemical radiation, preferably UV light and / or visible light, or heat. Therefore, the curing catalyst may be a catalyst for photocuring (photoinitiator) or a catalyst for thermal curing (thermosetting catalyst).

[0086] It may be advantageous for the composition of the present invention to contain one or more thermosetting catalysts. A thermosetting catalyst is a compound that generates reactive species, such as free radicals, cations, or anions, when exposed to heat. Preferably, the thermosetting catalyst includes organic peroxides such as 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (e.g., LUPEROX 101®), dilauroyl peroxide (e.g., LUPEROX LP®), dibenzoyl peroxide (e.g., LUPEROX A98®), and bis(tert-butyldioxyisopropyl)benzene (e.g., VulCUP R®). Such organic peroxides are available from a variety of sources, including but not limited to Arkema (France). Preferred 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 peroxyesters. Examples of thermosetting catalysts also include inorganic peroxides such as peroxydisulfates containing sodium persulfate (Na2S2O8), potassium persulfate (K2S2O8), and ammonium persulfate ((NH4)2S2O8). Examples of thermosetting catalysts further include azobisisobutyronitrile (AIBN).

[0087] It may be advantageous for the composition of the present invention to contain one or more photoinitiators. A photoinitiator is a compound that generates a reactive species, such as a free radical, cation, or anion, when exposed to chemical radiation, preferably UV light or visible light, more preferably UV light. Any suitable photoinitiators include Norish type I and Norish type II photoinitiators, and may, but are not limited to, commonly used UV photoinitiators, including, for example, acetophenone (e.g., diethoxyacetophenone), phosphine oxides, 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 by Rolland et al.). 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, which is available from IGM resins under the trademark name OMNIRAD® 819 (formerly known as IRGACURE® 819 from BASF SE). Other photoinitiators that may be used in the compositions of the present invention are available from IGM resins under the product names OMNIRAD® TPO (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide) and OMNIRAD® TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenylphosphineate). Nourish 1 type photoinitiators, such as benzophenone, benzoin, α-hydroxyalkylphenone, acylphosphine oxide, or derivatives thereof, are particularly preferred. Conventional photoinitiators are described, for example, in "A Compilation of Photoinitiators Commercially available for UV today" (K. Dietliker, SITA Technology Ltd., London 2002).

[0088] The amount of curing catalyst (component (d)) present in the composition of the present invention is preferably 0 to 5% by weight, preferably 0.1 to 3% by weight, and more preferably 0.5 to 2.5% by weight, based on the total weight of the sum of components (a) to (e) and / or based on the total weight of the composition.

[0089] Component (e) of the composition according to the present invention consists of one or more additives.

[0090] Component (e) may include solid particles suspended or dispersed therein as an additive. Any suitable solid particles can be used depending on the final product to be manufactured. The particles may be metallic, organic / polymeric, inorganic, or composites or mixtures thereof. The particles may be nonconductive, semiconductive, or conductive (including metallic and nonmetallic or polymeric conductors), and may be magnetic, ferromagnetic, paramagnetic, or nonmagnetic. The particles may be of any suitable shape, including spherical, elliptical, cylindrical, etc. The particles may be of any suitable size (e.g., in the range of average diameter 1 nm to 200 μm). The particles may contain active agents 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.

[0091] Component (e), here again, may include, as an additive, pigments, dyes, active compounds, and detectable compounds (e.g., fluorescence, phosphorescence), depending on the specific purpose of the product being manufactured.

[0092] It is particularly preferable that component (e) contains a light-absorbing, non-reactive pigment or dye as an additive. Preferred examples of such light absorbers include, but are not limited to, (i) titanium dioxide (e.g., included in amounts of 0.05 or 0.1 to 1 or 5 weight percent), (ii) carbon black (e.g., included in amounts of 0.05 or 0.1 to 1 or 5 weight percent), and / or organic ultraviolet light absorbers (UV blockers), e.g., hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxypenyltriazine, thiophene and / or benzotriazole ultraviolet light absorbers (e.g., Mayzo BLS1326) (e.g., included in amounts of 0.001 or 0.005 to 1, 2 or 4 weight percent). Examples of suitable organic ultraviolet light absorbers include, but are not limited to, those described in U.S. Patent Nos. 3,213,058, 6,916,867, 7,157,586, and 7,695,643, the disclosures of which are incorporated herein by reference. A further example of a suitable organic ultraviolet light absorber is 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (BBOT).

[0093] If the composition contains component (d) which contains a thermosetting catalyst, it is preferable that component (e) is also present and contains a curing accelerator for thermosetting. Examples of such curing accelerators include organic acid metal salts such as cobalt naphthenate, and N-substituted aromatic amines such as N,N-dimethylaniline and N,N-dimethyl-p-toluidine.

[0094] If the composition contains component (d) which contains a photoinitiator, it is preferable that component (e) is also present and contains 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.

[0095] The compositions according to the present invention may include any suitable filler as an additive (component (e)) depending on the desired properties of the part or object to be manufactured. Therefore, the filler may be solid or liquid, organic or inorganic, and may include, 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), inorganic fillers such as silicates (talc, clay, silica, mica, etc.), glass, carbon nanotubes, graphene, cellulose nanocrystals, and all combinations thereof. Suitable fillers may include, but are not limited to, reinforcing agents such as core-shell rubber. The filler is preferably selected from inorganic particles, more preferably from carbon black and / or silica. Most preferably, silica functionalized with methacrylate groups is present as a filler in the compositions according to the present invention. Suitable silica functionalized with methacrylate groups is available, for example, from Evonik Industries AG (Germany) under the trademark names AEROSIL® 701, AEROSIL® 711, AEROSIL® R 7200, and AEROSIL® R 8200. The amount of filler present in the composition of the present invention is preferably 0 to 20% by weight, preferably 0 to 10% by weight, and more preferably 0 to 5% by weight, based on the total weight of the sum of components (a) to (e) and / or based on the total weight of the composition.

[0096] The compositions according to the present invention preferably include a polymerization inhibitor and / or antioxidant as an additive (component (e)). By using a polymerization inhibitor and / or antioxidant, polymerization of the composition can be prevented during its preparation and / or storage. Suitable polymerization inhibitors include, 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-butylbenzol, 4-methoxy-2(3)-tert-butylphenol (BHA), BHA in combination with bis[2-carboxyethyl]sulfide (TDPA), 4-methyl-2,6-di-tert-butylphenol (BHT), bis[4- [Hydroxy-2-methyl-5-tert-butylphenyl] sulfide, 4-butyl mercaptomethyl-2,6-di-tert-butylphenol, 4-hydroxy-3,5-di-tert-butylphenylmethanesulfonic acid dioctadecyl ester, 2,5-dihydroxytoluene, 2,5-dihydroxy-1-tert-butylbenzene, 2,5-dihydroxy-1,4-di-tert-butylbenzene, 3,4-dihydroxy-1-tert-butylbenzene, and 2,3-dimethyl-1,4-bis[3,4-dihydroxyphenyl]butane, 2,2'-thiobis(4-tert-octylphenol), (2,2,6,6)-tetramethylpiperidine-1-yl)oxyl (TEMPO), and TEMPO derivatives such as 4-hydroxy-TEMPO. A preferred polymerization inhibitor is 2,6-di-tert-butyl-4-methylphenol (BHT), which is sold by Oxiris Chemicals SA under the trademark name IONOL® CP. The amount of polymerization inhibitor present in the composition of the present invention is preferably 0.001 to 1% by weight, more preferably 0.01 to 0.5% by weight, based on the total composition.

[0097] The total amount of additives (component (e)) present in the composition of the present invention is preferably 0 to 20% by weight, preferably 0 to 10% by weight, and more preferably 0 to 5% by weight, based on the total weight of the sum of components (a) to (e) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0098] Component (f) of the composition according to the present invention consists of one or more solvents. Examples of solvents 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 solvent-free. Therefore, it is preferable that the amount of solvent present in the composition of the present invention is 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 sum of components (a) to (e) and / or based on the total weight of the composition.

[0099] The compositions according to the present invention are preferably used to manufacture release coatings, protective films, protective coatings, or 3D printed objects by curing the compositions.

[0100] Therefore, it is preferable that the composition is curable, preferably curable by a radical reaction, which can be initiated thermally, by UV radiation, and / or by an electron beam. The composition according to the present invention can be three-dimensionally crosslinked by free radicals, for example by adding a peroxide, or by thermal curing in a very short time under the influence of high-energy radiation such as UV or an electron beam, to form a mechanically and chemically durable layer with adhesive properties that can be predetermined, taking into account a suitable formulation of the composition according to the present invention. When the radiation used is UV radiation, crosslinking / curing preferably occurs in the presence of a photoinitiator and / or a photosensitizer. Nourish 1 type photoinitiators, such as benzophenone, benzoin, α-hydroxyalkylphenone, acylphosphine oxide, or derivatives thereof, are preferred. Conventional photoinitiators are described, for example, in "A Compilation of Photoinitiators Commercially available for UV today" (K. Dietliker, SITA Technology Ltd., London 2002). A preferred composition according to the present invention contains a photoinitiator and / or photosensitizer in a mass proportion of 0.01% to 10%, particularly 0.1% to 5%, based on the mass of the total composition. The photoinitiator and / or photosensitizer is preferably soluble in the composition according to the present invention, and more preferably soluble in a mass proportion of 0.01% to 10%, particularly 0.1% to 5%, based on the mass of the total composition.

[0101] The compositions according to the present invention can be prepared by any preferred method, for example, by mixing component (a) with one or more optional components (b) to (f) in any order. The solvent (component (f)) is used primarily to reduce the viscosity of the composition and to facilitate the mixing of the components. Component (f) facilitates the manufacture and application of the composition. However, it is generally preferable to provide a composition that is essentially solvent-free, i.e., essentially component (f)-free. Consequently, it is preferable to remove the solvent (component (f)) from the composition (essentially) after its preparation or at some point during its preparation.

[0102] Therefore, a further aspect of the present invention is: (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 components (b) to (e), preferably component (b) and / or (c), to the mixture of step (i). (iii) A step of (essentially) removing component (f) from the mixture of step (ii), (iv) A step of preparing a mixture by optionally adding at least one of components (b) to (e) to the mixture of step (iii) if the component was not added in step (ii). A method for preparing a composition according to the present invention, which includes or comprises the following.

[0103] Steps (i) to (iv) of the method are carried out in a predetermined order. However, these may be interrupted by additional intermediate steps. In addition to the solvent component (g), or as a substitute for the solvent (component (g)), a reactive diluent (component (b)) may also be used. The preparation of the mixture may be carried out at room temperature or at high temperatures. Mixing may be carried out using a conventional mixing device, such as a speed mixer.

[0104] The composition according to the present invention can be used in a variety of fields. This composition is particularly suitable for use in the production of release coatings, protective films, and protective coatings, as well as in the manufacture of 3D printed objects by stereolithography.

[0105] Therefore, a further aspect of the present invention is a release coating, protective film, or protective coating that can be obtained by curing the composition according to the present invention, or a 3D printed object that can be obtained by 3D printing the composition according to the present invention.

[0106] It is preferable to use the composition according to the present invention to produce a release coating. Release coatings (often also called adhesive coatings) are known from the prior art. They are used in various methods for producing labels, adhesive tapes, or sanitary articles. Release coatings are characterized by low adhesion in contact with adhesives and consist of radiation-curable silicones. Two mechanisms are typically used for curing functional silicones. In the case of cationic curing, epoxy functional organosiloxanes are polymerized using a photoinitiator that releases acid upon irradiation. In the case of free radical curing, silicone (meth)acrylates are polymerized using a photoinitiator that forms radicals upon irradiation.

[0107] It is also preferable to use the compositions according to the present invention for 3D printing. "3D printing" is often referred to as "additive manufacturing," and vice versa. Therefore, in the context of this invention, the terms "3D printing" and "additive manufacturing" are used synonymously and refer to a method of constructing an object by adding multiple layers of material. An object obtained in this way is referred to as a 3D printed object in the context of this invention. It is preferable that the 3D printing method / additive manufacturing method is a method of producing an object from three-dimensional digital information.

[0108] Lithography-based additive manufacturing, such as stereolithography, is generally used, like 3D printing methods, primarily to produce prototypes and functional patterns ("rapid prototyping"). With technological advancements, actual production applications, such as transparent orthodontic or hearing aid shells, are becoming increasingly important. In these applications, the mechanical and thermal properties of the printed material are crucial. However, materials currently available for additive manufacturing do not yet possess the mechanical properties of conventional manufacturing materials (see, for example, T. Swetly, J. Stampfl, G. Kempf, and R.-M. Hucke, "Capabilities of Additive Manufacturing Technologies (AMT) in the Validation of the Automobile Cockpit," RTejournal - Forum for Rapid Technology 2014 (1)).

[0109] These materials (resins) for lithography-based additive manufacturing are based on reactive components that can be cured upon exposure. For this purpose, radical (e.g., acrylate) or cationic (e.g., epoxide) polymerization is frequently used. For this purpose, special photoinitiators are added to the resin, and these photoinitiators cause polymerization of the reactive components by changing their state upon exposure.

[0110] Various methods are available for additive manufacturing of objects from these resins, including stereolithography, digital photoprocessing, and multi-jet modeling. All procedures involve layering and curing these resins to produce three-dimensional objects. Generally, resins with low viscosity, e.g., 20–40 mPa·s, are required (see I. Gibson, DW Rosen, B. Stucker et al., "Additive manufacturing technologies", vol. 238, Springer Verlag (2010)). To improve the mechanical properties of the cured products, particularly toughness and elongation at break, the crosslinking density can be reduced or the molecular weight of the monomers can be increased. However, this increases the viscosity or melting point of the uncured resin, and until recently, for the latter reason, these could not be cured using additive manufacturing methods. Furthermore, the curing rate can become too slow.

[0111] However, new developments will make it possible to process resins with higher viscosity. For example, International Publication Nos. 2015 / 075094 and 2016 / 078838 describe stereolithography devices that can process even high-viscosity resins by heating sequentially cured layers of polymerizable material. International Publication No. 2015 / 074088 describes a photopolymerizable composition having a viscosity of at least 20 Pa·s at room temperature, which is heated to at least 30°C during curing. For comparison, 20 Pa·s is roughly equivalent to the viscosity of ethylene glycol or viscous honey, while butter with a viscosity of about 30 Pa·s is hardly flowable. However, this is advantageous when it is not necessary to heat the polymerizable material during the addition process.

[0112] The compositions of the present invention exhibit low viscosity, rapid photocuring reaction, and good mechanical properties, particularly with respect to tensile strength at fracture and elongation at fracture.

[0113] The composition used in this invention has the advantage of being able to 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.

[0114] The compositions used in this invention have the advantage of being able to be processed without the presence of a solvent. Therefore, no organic volatile substances are generated during the addition process.

[0115] The compositions used in this invention have the further advantage of being able to be produced by a simple method.

[0116] The compositions used in the present invention have the advantage of potentially containing fillers that provide better properties, particularly better tensile strength and elongation at the break.

[0117] The compositions used in this invention have low T g The composition comprises a polymer (reaction product) having the following properties, and the use of this composition has the further advantage that an elastomer, or a product having one or more properties typical of elastomers, for example, a break point elongation of preferably more than 40%, more preferably more than 60%, and most preferably more than 100%, can be obtained by addition.

[0118] The compositions according to the present invention can preferably be used as photopolymerizable materials in additive manufacturing / 3D printing methods based on stereolithography. In particular, the compositions according to the present invention can be applied as raw materials in additive manufacturing methods such as those described in International Publication No. 2015 / 075094 or International Publication No. 2016 / 078838.

[0119] Generally, additive manufacturing / 3D printing methods are based on the following technique: processing multiple layers of photopolymerizable material to create an object. In this method, newly supplied layers of photopolymerizable material are polymerized with a desired contour in each case, and by continuously defining the individual contour of each layer, the desired object is formed with its three-dimensional shape obtained from the series of fabricated layers.

[0120] Therefore, a method for preparing a peel-off coating or a 3D printed object preferably consists of the following indirect or direct sequence of steps: a. Step of applying the composition to the surface, b. A step of curing the composition, preferably by irradiation with UV radiation. Includes.

[0121] In the generation of a 3D printed object by a 3D printing method, steps a and b are preferably repeated in an alternating order. In this way, the 3D printed object is constructed step by step.

[0122] Suitable UV radiation sources for curing the compositions according to the present invention are optionally doped medium-pressure mercury vapor lamps, low-pressure mercury vapor lamps, UV-LED lamps, or so-called excimer emitters. The UV emitter may be multicolored or monocolored. The emission range of the emitter is preferably within the absorption range of the photoinitiator and / or photosensitizer.

[0123] In the formation of the release coating, the surface is preferably the surface of a carrier, preferably a sheet-like carrier. Here, the composition of the present invention can be applied to one side 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 have a surface structure. Particularly preferred carriers are polypropylene film and polyethylene film.

[0124] Release coatings are applied, for example, to adhesive tapes, labels, packaging for self-adhesive sanitary products, food packaging, self-adhesive thermal paper, or liners for asphalt roofing films. Release coatings have a good release effect on adhesive materials used in these applications.

[0125] The peel effect of adhesive materials, typically adhesive tapes or labels for industrial applications, is expressed by the peel strength, with a low peel strength indicating a good peel effect. The peel strength is determined according to the FINAT Handbook 8th Edition, The Hague / NL, 2009, designated FTM10, with the added modification that storage is performed under pressure at 40°C. The peel strength depends on the quality of the peel coating (e.g., uniformity, thickness, and / or smoothness of the coating), the adhesive material or bonding agent, and the test conditions. Therefore, for the evaluation of the peel coating, the adhesive or bonding agent and test conditions should be the same. The peel strength is verified using TESA® 7475 adhesive tape, 2.5 cm wide, a trademark of Tesa SE, Germany, Hamburg.

[0126] The peelable coating of the present invention preferably has a peeling force of up to 20 cN / 2.5 cm, more preferably up to 10 cN / 2.5 cm, and very preferably up to 8 cN / 2.5 cm, with a peeling force of at least 0.5 cN / 2.5 cm, and preferably at least 1 cN / 2.5 cm.

[0127] Those skilled in the art will likely be able to make full use of the foregoing description without further detail. Therefore, preferred embodiments and examples should be interpreted as merely explanatory disclosures and not as limiting in any way.

[0128] Those skilled in the art will likely be able to utilize the foregoing description to the fullest extent possible without further detail. Therefore, preferred embodiments and examples should be interpreted as merely explanatory disclosures and not as limiting in any way.

[0129] All definitions, embodiments, and details applicable to one aspect of the present invention are applicable to other aspects of the present invention with necessary modifications, and vice versa.

[0130] The subject matter of the present invention will be described in more detail with reference to Figures 1 and 2, but it is not intended that the subject matter of the present invention is limited thereto. [Brief explanation of the drawing]

[0131] [Figure 1] The reaction scheme for the synthesis of silicone urethane (meth)acrylate (7) according to formula (A), which is formed by the reaction of hydroxy-functional silicone (meth)acrylate (5) and isocyanate-functional urethane (meth)acrylate (6), is shown, wherein hydroxy-functional silicone (meth)acrylate (5) is formed by the reaction of (meth)acrylic acid (1) and epoxy-functional silicone (2), and isocyanate-functional urethane (meth)acrylate (6) is formed by the reaction of diisocyanate (3) of formula (D) and hydroxy-functional (meth)acrylate (4) of formula (E). [Figure 2] The tensile (dotted line) and cyclic (solid line) measurements of 3D-printed test samples based on formulations F16 and F17 are shown.

[0132] The present invention will be illustrated in the following examples, but the scope of the invention is clear from the entire specification and claims and there is no possibility that it should be interpreted as being limited to the embodiments described in the examples. Therefore, the following examples are for the sole purpose of detailing the invention to those skilled in the art and do not constitute any limitation of the claimed subject matter.

[0133] Examples The following embodiments are for the sole purpose of detailing the invention to those skilled in the art and do not constitute any limitation of the claimed subject matter.

[0134] method Epoxy value: The epoxide value was determined in weight percent according to DIN EN ISO 3001 (1999-11) and ASTM D 1652 (2011).

[0135] 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)).

[0136] Acid value: The acid value was determined in mgKOH / g polymer by titration according to DIN EN ISO 2114 (2002-06).

[0137] Hydroxyl value (OH value): The OH value was determined in mgKOH / g polymer by titration according to DIN EN ISO 4629-2 (2016-12).

[0138] Isocyanate value (NCO value): The NCO value was determined in weight percent by titration according to DIN EN 1242 (2013-05).

[0139] Gel permeation chromatography (GPC): Weight-average molecular weight Mw and number-average molecular weight M n The GPC measurement was performed under the following conditions: column combination SDV1000 / 10000Å (length 55cm), temperature 35℃, THF as mobile phase, flow rate 0.35ml / min, sample concentration 10g / l, RI detector, and evaluation of polymer relative to polystyrene standard (162-2520000g / mol).

[0140] material VESTANAT(registered trademark) 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: [ka] Component (a) - Silicone urethane (meth)acrylate according to formula (F)

[0141] synthesis S1) Preparation of silicone urethane acrylate by 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) A 2 L four-necked flask equipped with a mechanical stirrer, reflux condenser, and internal thermometer is loaded with 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 50% aqueous chromium(III) acetate while stirring. 1291 g of polydimethylsiloxane with a 1.32 wt% epoxide oxygen number, modified with terminal epoxy groups, is added while heating to 115°C. Stirring at 115-120°C is continued until more than 99% of the epoxy group conversion, determined by the acid number, is achieved. All volatile substances are then removed by distillation at 120°C under complete vacuum. Filtration yields a liquid silicone acrylate with a viscosity of less than 200 mPa·s and a hydroxyl number of 52 mg KOH / g at 25°C.

[0142] In a 2 L four-necked flask equipped with a mechanical stirrer, reflux condenser, and 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 had a residual NCO content of less than 0.03% and a number-average molecular weight M determined by GPC at 4395 g / mol. n It also has a weight-average molecular weight Mw of 6513 g / mol.

[0143] S2) Preparation of silicone urethane acrylate by 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 =Equation (J), and R A =Formula (K) or (L) In a 2 L four-necked flask equipped with a mechanical stirrer, reflux condenser, and internal thermometer, 253 g of 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 had a viscosity of 1837 mPa·s at 25°C and a number-average molecular weight M determined by GPC at 2872 g / mol. n It also has a weight-average molecular weight Mw of 5377 g / mol.

[0144] S3) Preparation of silicone urethane acrylate by 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, R 1 =H, R 2 =Formula (H), R 3=Formula (I), R 4 =H, and R 5 =Formula(J) A 2 L four-necked flask equipped with a mechanical stirrer, reflux condenser, and internal thermometer is loaded with 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 European Patent Application Publication No. 3168273, and 1.7 g of 50% aqueous chromium(III) acetate, while stirring. To this, 2763.5 g of polydimethylsiloxane with a 0.92 wt% epoxide oxygen number modified with terminal epoxy groups is added while heating to 115 °C. Stirring at 115-120 °C is continued until more than 99% of the epoxy group conversion, determined by the acid number, is achieved. All volatile substances are then removed by distillation at 120 °C and under a vacuum of 3 mbar by small amounts of extraction. Filtration yields a liquid silicone acrylate with a hydroxyl value of 30 mg KOH / g.

[0145] In a 2 L four-necked flask equipped with a mechanical stirrer, reflux condenser, and internal thermometer, 3140.8 g of the silicone acrylate thus prepared was mixed with 1123.5 g of acetone, 604.2 g of VESTANAT® EP-DC 1241, and 7.5 g of TIB KAT 716 LA, and stirred at 60°C for 6 hours. Distillation at 60°C and 3 mbar with a small amount of extraction yielded a clear, greenish-brown product with a viscosity of 18216 mPa·s at 25°C.

[0146] S4) Preparation of silicone urethane acrylate by formula (F), where 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, R 5 =Formula(J) A 5 L four-necked flask equipped with a mechanical stirrer, reflux condenser, and internal thermometer is loaded with 47.7 g of hydroxy-functional siloxane having a hydroxyl value of 200 mg KOH / g, prepared according to Example 1 of European Patent No. 0940422, and 57.7 g of VESTANAT® EP-DC 1241. The mixture is heated to 80°C while stirring. 0.21 g of TIB® KAT 716 LA is added, and the mixture is stirred at 80°C for 5 hours. During this time, the viscosity increases rapidly. This yields a polymer that is clear and yellow, has high viscosity at 80°C, and solidifies into a glassy mass at room temperature.

[0147] S5) Preparation of silicone urethane acrylate by formula (F), where 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, R 5 =Formula(J) In a 5L four-necked flask equipped with a mechanical stirrer, a reflux condenser, and an internal thermometer, 1055.21 g of hydroxy-functional siloxane having a hydroxyl value of 42 mg KOH / g, prepared by the prior art disclosed in European Patent No. 0940422, 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.

[0148] The reaction mixture is heated to 60°C and stirred for 4 hours. Toluene is removed by distillation at 70°C, and after 2 hours, when the target pressure of 20 mbar is reached, a polymer is obtained that is very viscous at 70°C and solidifies into a glassy mass at room temperature. The number average molecular weight M was determined by GPC. n The molecular weight is 8638 g / mol, and the weight-average molecular weight Mw is 28731 g / mol.

[0149] S6) Preparation of silicone urethane acrylate by 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, R 5 =Formula(J) A 0.5 L four-necked flask equipped with a mechanical stirrer, reflux condenser, and internal thermometer is loaded with 179.0 g of polydimethylsiloxane modified with terminal hydroxyl groups and having a hydroxyl value of 47 mg KOH / g. 53.3 g of VESTANAT® EP DC 1241 and 116.1 g of toluene are added while stirring. 0.23 g of TIB® KAT 716 LA is then added. The reaction mixture is heated to 60°C and stirred at 60°C for 4 hours. The solvent is then removed in a rotary evaporator at 80°C and 2 mbar for 1 hour. A highly viscous polymer that solidifies at room temperature is obtained.

[0150] S7) Preparation of silicone urethane acrylate by 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) A 0.5 L four-necked flask equipped with a mechanical stirrer, reflux condenser, and internal thermometer is loaded with 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 European Patent Application Publication No. 3168273, and 0.19 g of 50% aqueous chromium(III) acetate, while stirring. To this, 303.7 g of linear polydimethylsiloxane with a 0.79 wt% epoxide oxygen number, modified with one terminal epoxy group and one terminal trimethylsiloxy group, is added while heating to 120°C. Stirring at 115-120°C is continued until more than 99% of the epoxy group conversion, determined by the acid number, is achieved. Next, all volatile substances are removed by distillation at 120°C and under a vacuum of 3 mbar with a small amount of extraction. By filtration, a liquid silicone acrylate with a hydroxyl value of 27 mg KOH / g is obtained.

[0151] In a 0.5 L four-necked flask equipped with a mechanical stirrer, reflux condenser, and internal thermometer, 200.6 g of the silicone acrylate thus prepared was mixed with 70.3 g of acetone, 33.8 g of VESTANAT® EP-DC 1241, and 0.23 g of TIB KAT 716 LA, and stirred at 60°C for 4 hours. Distillation at 60°C and 1-2 mbar with a small amount of extraction yielded a greenish, clear product with a viscosity of 857 mPa·s at 25°C.

[0152] S8) Preparation of silicone urethane acrylate by formula (F), where 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) In a 2 L four-neck flask equipped with a mechanical stirrer, a reflux condenser, and an internal thermometer, 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 European Patent Application Publication No. 3168273, and 0.422 g of a 50% aqueous chromium(III) acetate solution are charged while stirring. To this, while heating to 115 °C, 666.64 g of a statistically distributed [poly-dimethyl(methyl-, glycidoxypropyl)] siloxane-copolymer having an epoxy oxygen value of 1.08% by weight and a viscosity of 145 mPa·s at 25 °C is added. Stirring at 115 to 120 °C is continued until the conversion of epoxy groups, as determined by the acid value, exceeds 99%. Then, all volatile substances are distilled off at 120 °C and 3 mbar under a slight vacuum by pumping. By filtration, a liquid silicone acrylate having a hydroxyl value of 33.8 mgKOH / g is obtained.

[0153] In a 1 L four-neck flask equipped with a mechanical stirrer, a reflux condenser, and an internal thermometer, 215.8 g of the silicone acrylate thus prepared is mixed with 77.9 g of acetone, 43.9 g of VESTANAT® EP-DC 1241, and 0.25 g of TIB KAT 716 LA and stirred at 60 °C for 4 hours. By distillation at 60 °C and 3 mbar under a slight vacuum by pumping, a brown transparent product having a viscosity of 20004 mPa·s at 25 °C is obtained.

[0154] S9) Preparation of a silicone urethane acrylate according to formula (F), wherein m1 = 2, m2 = 0, m3 = 0, d1 = 65, d2 = 2, d3 = 2, 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) In a 1 L four-neck flask equipped with a mechanical stirrer, a reflux condenser, and an internal thermometer, 183.6 g of the silicone acrylate prepared in Example S8 is mixed with 60.7 g of acetone, 18.7 g of VESTANAT® EP-DC 1241, and 0.20 g of TIB KAT 716 LA and stirred at 60°C for 4 hours. By distillation at 60°C and 3 mbar with a little evacuation, a brown transparent product having a viscosity of 2146 mPa·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 that are not according to the present invention.

[0156] [Table 1]

[0157] [Table 2]

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

[0159] [Table 3]

[0160] Component (c) - silicone (meth)acrylate without urethane groups Component (c1): silicone (meth)acrylate according to formula (Q) The silicone (meth)acrylates S10, S12, and S13 according to formula (Q) are prepared by a prior art method as described, for example, in European Patent Application Publication No. 0940422. The silicone (meth)acrylates according to formula (Q) are listed in Table 3.

[0161]

Table 4

[0162] Component (c2): silicone (meth)acrylate according to formula (S) The silicone (meth)acrylate according to formula (S) is prepared by a prior art method as disclosed, for example, in European Patent Application Publication No. 3168273 or International Publication No. 2017187030. The silicone (meth)acrylate according to formula (S) is listed in Table 4.

[0163]

Table 5

[0164] Preparation of a mixture containing organic acrylates On the premise that this is acceptable in terms of viscosity, the resulting silicone urethane (meth)acrylate is mixed with an organic acrylate as a reactive diluent while heating and stirring. In the case of a low-boiling or heat-sensitive reactive diluent, the diluent exchange is carried out immediately after the synthesis. This is done, in individual cases, by adding the required amount of organic (meth)acrylate (reactive diluent) to the desired mixture and distilling off acetone at room temperature under full vacuum. The mixture according to the invention is shown in Table 5.

[0165]

Table 6

[0166] Hardening test UV-curable silicone or a blend thereof was mixed with 2 wt% of the photoinitiator TEGO® A18. 30 g of this mixture was placed on a 5 cm diameter aluminum lid to obtain a layer several millimeters thick. The lid was placed under an 80 W / cm mercury UV lamp from Eltosch. Curing generally occurred within a few seconds. The test specimens were left at room temperature for one day, and then visually inspected and tested for surface abrasion and tackiness. If there were no problems in terms of the mechanical stability of the test specimens, they were removed from the lid and subjected to manual bending and tearing. The mixtures used in the curing tests are shown in Table 6.

[0167] [Table 7]

[0168] The curing test results clearly show that the cured composition based on silicone urethane (meth)acrylate according to the present invention has superior properties compared to the composition based on silicone (meth)acrylate without urethane groups. The cured composition according to the present invention exhibits a smooth surface and is bendable, while compositions not according to the present invention have either a soft, sticky surface or a wrinkled surface. Furthermore, compositions not according to the present invention fail the tear test.

[0169] Casting Test The mechanical properties of the silicone were evaluated by measuring the cured formulations prepared by casting. Crosslinking was induced by adding 1% by weight of a photoinitiator (TPO-L) and irradiating the composition with a UV lamp or projector. The components of the formulation were weighed on a balance with an accuracy of ±0.001 g and homogenized in a SpeedMixer at 2300 rpm for 10 minutes. The volume was set according to the required volume. During mixing, the entire setup was heated to 40°C. The formulations were named FX (X = test number).

[0170] The viscosity (η) of the uncured sample was measured using a Malvern Kinexus Lab+ rheometer with a cone-plate shape (4°) after equilibration at room temperature (RT). The reported values ​​were obtained using a frequency of 10 Hz.

[0171] The cast sample is exposed to UV radiation with a wavelength of 405 nm (2400 mW / cm²). 2 The mixture was prepared after exposure to light. The exposure time was 5 minutes. The object was then washed in isopropanol for 10 minutes and placed in a curing station at 80°C for 2 hours (light intensity 18 mW / cm²). 2 (and wavelength 405 nm).

[0172] The mechanical properties of the cured samples were evaluated using a universal testing machine in accordance with DIN EN ISO 527 5A. Where used herein, "DIN EN ISO 527 5A" refers to the test conditions of DIN EN ISO 527, as described in Part 1 of the aforementioned standard, and tests are conducted on specimens having the size and shape corresponding to "5A" as described in Part 2 of the aforementioned standard. The parameters of interest are Young's modulus (E) and tensile strength at fracture (σ). b ), and elongation at fracture (ε b )

[0173] Table 7 shows the components, content (%), and mechanical properties of the evaluated formulations.

[0174] [Table 8]

[0175] As shown in Table 7, the combination of silicone urethane (meth)acrylate and silicone (meth)acrylate without urethane groups according to the present invention makes it possible to obtain an elastomer material that is highly elastic and can recover its original shape after deformation. It is also clear that by simply adjusting the amounts of silicone urethane (meth)acrylate, silicone (meth)acrylate without urethane groups, and organic (meth)acrylate according to the present invention, it is easy to match the required viscosity and mechanical properties. Furthermore, from the comparison of F12 and F14, and F13 and F15, it is clear that a composition based on silicone urethane acrylate S1 (having 4 acrylate groups and 4 urethane groups) yields an elastomer material with better mechanical properties compared to a similar composition based on silicone urethane acrylate S7 (having 2 acrylate groups and 2 urethane groups).

[0176] Additive manufacturing using stereolithography (SLA) and digital photolithography (DLP) Generally, formulations can be printed using SLA or DLP printers with projectors of wavelengths between 365 and 405 nm. In the following example, the power is 15 mW / cm². 2 The formulation was processed using a DLP printer (Station 5, Atum3D) equipped with a projector having a light intensity and a wavelength of 405 nm. To ensure the fluidity of the material while the construction platform is moving, the viscosity of the formulation should not exceed 30,000 mPa·s. Table 8 shows examples of the most important parameters for the print job.

[0177] [Table 9]

[0178] Table 9 shows the composition of the test specimens according to standard DIN EN ISO 527 5A. The photographic packaging was adapted to the printer's wavelength and light intensity (photoinitiator: 1-2 wt%, UV blocker: 0.01-0.05 wt%). After printing, all objects were washed in isopropanol for 10 minutes and placed in a curing station at 80°C for 2 hours (light intensity: 18 mW / cm²). 2 (and wavelength: 405 nm).

[0179] [Table 10]

[0180] As shown in Table 9, DLP of formulations containing silicone urethane (meth)acrylate and silicone (meth)acrylate without urethane groups makes it possible to obtain highly elastic elastomer materials that can recover their original shape after deformation. F10, F11, F12, and F13 showed that adding silicone urethane acrylate (L) to silicone acrylate (S13 or S12) converts the material into an elastomer (E). From rigid formulations (F1) or flexible formulations (F6, F7, F8, and F9) to rubbery materials, their initial shape can be recovered. F10 vs. F11 showed that increasing the S1 content increased tensile strength and Young's modulus. These results are similar to those for F12 vs. F13. The addition of organic (meth)acrylate (IBOMA) improves printability. Furthermore, this monomer has a high glass transition temperature (T g ) is present, thereby increasing the tensile strength and Young's modulus of the soft (S) sample. Furthermore, from a comparison of F12 and F14, as well as F13 and F15, it is clear that compositions based on silicone urethane acrylate S1 (having 4 acrylate groups and 4 urethane groups) result in elastomer materials with better mechanical properties compared to similar compositions based on silicone urethane acrylate S7 (having 2 acrylate groups and 2 urethane groups).

[0181] Cycle measurement of printed silicone formulations To demonstrate the suitability of silicone urethane acrylate (S1) for producing elastomer (E) materials, cycle measurements were performed to determine the material's recovery rate after elongation. Table 10 shows the composition, viscosity, and mechanical properties of the samples. The samples were printed according to the procedures previously described in the section on additive manufacturing using stereolithography (SLA) and digital photolithography (DLP).

[0182] Tensile tests were performed according to the standard DIN EN ISO 527 5A. For comparison purposes, the same test conditions were maintained in cycle measurements. In each cycle, the sample was deformed to half of its elongation at break (εb) as shown in Table 10. The procedure was as follows: - In the case of F16, the maximum force of 11.6N is applied first. Then, the force is reduced to 1.1N.

[0183] - In the case of F17, apply the maximum force of 5N first. Then, reduce the force to 0.7N.

[0184] This cycle was repeated 10 times. None of the test specimens failed during the cycle measurement. The recovery time for each cycle was calculated as follows: Recovery (%) = (ε max -ε min ) × 100 / ε max In the formula, ε max ε refers to the maximum growth observed during each cycle. min This refers to the minimum growth observed during each cycle.

[0185] The results of the cycle measurements are shown in Table 11 and Figure 2. For F16, recovery is 52% in the first cycle and 44% in the tenth cycle. This behavior shows typical plastic deformation and irrecoverable deformation for the flexible material (F). Clearly, the yield point is above the mechanical curve (plot on the left), and with each cycle, displacement occurs, reducing the recovery value and showing further plastic deformation. In contrast, for F17, recovery is 89% in the first cycle and 87% in the tenth cycle, with almost no displacement. The elastomer material (E) typically does not show a yield point. This indicates that the flexible material (F) can be converted to the elastomer material (E) by adding S1 to the formulation.

[0186] [Table 11]

[0187] curing kinetics Curing kinetics were evaluated by measuring the curing depth (layer thickness) of resins exposed to irradiation at different time intervals. Resin thickness (curing depth) was measured using a gauge length with an accuracy of ±1 μm. The formulation was placed on a microscope slide and irradiated using a projector from a DLP printer (light intensity: 15 mW / cm²). 2 (Wavelength: 405nm). Remove excess resin and measure the thickness.

[0188] Formulas F4, F8, and F12 corresponding to S1, S12, and S1 / S12 mixtures were compared. Table 12 shows the selected formulas from Table 7. The reported curing time is the first time the layer is measured, and the curing depth is the amount of thickness this layer was able to cure within the time mentioned.

[0189] [Table 12]

[0190] Table 12 clearly shows that the silicone urethane (meth)acrylate of the present invention results in an increase in curing depth and a decrease in curing time (i.e., an increase in curing speed). Therefore, silicone urethane (meth)acrylate can be used to facilitate 3D printing methods.

[0191] Table 13 shows the time dependence of the curing depth after exposure of the resin to UV irradiation. The target printing speed will likely be determined by the curing time.

[0192] [Table 13]

[0193] F4 showed a curing depth of 390 μm in 5 seconds. At the same time interval, F8 showed a curing depth of zero. F8 required at least 60 seconds to show 73 μm. The curing efficiency of S1 in F4 (very hard) is better than that of S12 in F8 (flexible). Compared to F8, a mixture of S1 and S12 in F12 (elastomer) can reduce the required curing time to 10 seconds and increase the curing depth to 117 μm. By including 10 wt% of S1, curing efficiency is improved, printing speed is increased, and more parts can be produced per minute.

[0194] Coating removal Preparation of the peel-off 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, particularly in the form of an adhesive coating on a sheet-like carrier, specifically within such a carrier, for use in adhesive tapes or label laminates.

[0195] The formulation for the peel-off coating is prepared in all cases 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® A 18 (Evonik Industries AG, Germany).

[0196] The coating composition prepared in this manner is applied to a sheet-like carrier. This consists of a 50 cm wide biaxially oriented polypropylene film (BoPP), which in all cases was subjected to corona pretreatment with a 1 kW generator output before the application of the coating composition. The coating composition was applied at a rate of approximately 1 g / m² using a 5-roll coating unit from COATEMA® (Coating Machinery GmbH, Dormagen, Germany). 2 The coating is applied by weight and cured by exposure to UV light from a medium-pressure mercury lamp from IST® Metz GmbH (Nuertingen, Germany) in a nitrogen atmosphere with a residual oxygen content of less than 50 ppm at a belt speed of 60 W / cm and 100 m / min.

[0197] The coated test specimens are then scraped off and subjected to tests for peel strength and residual adhesion.

[0198] Scrub off: The adhesion of the cured coating to the carrier material is checked by rubbing the coating vigorously with a thumb. If the adhesion is insufficient, the rubbing will result in the formation of rubbery debris. Such debris should not be formed, even with vigorous rubbing. The test is performed by a trained panel. The results are evaluated on a scale of 1 to 5, where 1 is very good and 5 is fairly poor adhesion to the carrier material.

[0199] Separation force: The release effect of adhesive materials, typically in the form of adhesive tapes or labels for industrial applications, is expressed by the release force (RF), with a low RF indicating a good release effect. The release force depends on the quality of the release coating, the adhesive itself, and the test conditions. Therefore, the same adhesive and test conditions should be used when evaluating release coatings. To determine the release force, the laminate of adhesive tape or label is cut to a width of 2.5 cm, and then the adhesive surface is applied to a silicone coating in both cases for testing. This test is performed according to test protocol FTM 10 of the FINAT Handbook, 8th Edition, The Hague / NL, 2009, with the modification that storage is at 40°C under pressure. The adhesive tape used is tesa® 7475 (a trademark of Tesa SE, Hamburg, Germany). The reported values ​​are the average of five measurements and are reported in units of cN / 2.5cm.

[0200] Residual adhesive strength: Residual Adhesion (RAF) is determined by test protocol FTM 11 of the FINAT Handbook 8th Edition, The Hague / NL, 2009, differing in that the test adhesive strip in contact with the silicone is stored for a period of 1 minute, and the standard surface is an untreated BoPP surface. The adhesive tape used is tesa® 7475 (trademark of Tesa SE, Hamburg, Germany). Residual Adhesion is a measure of the crosslinking of the silicone. If there are movable silicone components due to the non-polymerization, the value of residual adhesion decreases as the proportion of such components increases. The results for the abrasion test, peel strength, and residual adhesion (RAF) are presented in Table 14.

[0201] [Table 14]

[0202] Table 14 clearly shows that Example S1 according to the present invention enables good adhesion along with an acceptable peel force. Adhesion to the substrate is also good.

[0203] Therefore, the components prepared according to the present invention satisfy all the important requirements for use in release coatings. By adjusting them appropriately for each system, they can be used either as adhesive components or as components with moderate to high release strength.

Claims

1. - At least three (meth)acrylate groups, - Urethane groups that are not more numerous than (meth)acrylate groups A silicone urethane (meth)acrylate having, The aforementioned silicone urethane (meth)acrylate Formula (A): 【Chemistry 1】 It includes the base of, During the ceremony, In all cases, Z1 is independently selected from the group consisting of CH3 or H. Z2 is a divalent organic radical, Z3 is a (q+1) valence organic radical, where q is an integer organic radical between 1 and 3. In all cases, Z4 is independently selected from the group consisting of -CH3 and -H, In the equation, each dotted line represents a covalent bond. The aforementioned silicone urethane (meth)acrylate Formula (F): M m1 M UA m2 M A m3 D d1 D UA d2 D A d3 T t Q q Formula (F) Represented by, 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 ], 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, During the ceremony, In each case, R is independently selected from the group consisting of monovalent organic radicals that do not have any urethane or (meth)acrylate groups. In each case, R UA is independently selected from the group consisting of monovalent organic radicals having at least one (meth)acrylate group and at least one urethane group. A silicone urethane (meth)acrylate characterized in that, 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.

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

3. Formula (B): X (-Y) ｐ Formula (B) Represented by, During the ceremony, X is a p-valent silicone radical, Y is bonded to the silicon atom of the silicon radical, In either case, a monovalent organic radical having at least one urethane group and at least one (meth)acrylate group is independently selected from the group, p is an integer of at least 1. A silicone urethane (meth)acrylate according to claim 1 or 2, characterized in that it is a silicone urethane (meth)acrylate.

4. Formula (C): [R ａ Y ｂ SiO （４－ａ－ｂ）／２ formula (C) Includes units represented by 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 contain any urethane groups. In each case, Y is independently selected from the group consisting of monovalent organic radicals having at least one urethane group and at least one (meth)acrylate group. A silicone urethane (meth)acrylate according to claim 1 or 2, characterized in that it is a silicone urethane (meth)acrylate.

5. Y is given by equations (M), (N), (O), and (P): 【Chemistry 2-1】 【Chemistry 2-2】 The silicone urethane (meth)acrylate according to claim 3, characterized by being represented by at least one of the following.

6. A method for preparing a silicone urethane (meth)acrylate according to claim 1 or 2, wherein the silicone urethane (meth)acrylate is formed by a reaction between at least one hydroxy-functional silicone (meth)acrylate and at least one isocyanate-functional urethane (meth)acrylate.

7. The method according to claim 6, characterized in that the hydroxy-functional silicone (meth)acrylate is formed by the reaction of at least one epoxy-functional silicone with (meth)acrylic acid and / or at least one hydroxy-functional (meth)acrylate.

8. The following ingredients: (a) At least one silicone urethane (meth)acrylate according to claim 1 or 2, (b) Optionally, at least one organic (meth)acrylate that does not contain any silicon atoms, (c) Optionally, at least one silicone (meth)acrylate that does not have any urethane groups, (d) Optionally, at least one curing catalyst, (e) Optionally, at least one additive, (f) At least one solvent, optionally. A composition containing or consisting of the following.

9. Based on the total weight of components (a) to (f) and / or based on the total weight of the composition, - 5 to 100% by weight of at least component (a), - At least component (b) in 0 to 60% by weight, - At least component (c) in 0 to 95% by weight, - Component (d) of 0-5% by weight, - 0-20% by weight of component (e), - Components (f) in amounts of 0 to 10% by weight The composition according to claim 8, comprising or consisting of the following.

10. 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 ]、 m1 is an integer of 2, d1 is an integer between 1 and 10000. During the ceremony, In each case, R is independently selected from the group consisting of monovalent organic radicals that do not have any urethane or (meth)acrylate groups. R Ａ However, in either case, a monovalent organic radical having at least one (meth)acrylate group but no urethane groups is independently selected from the 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 ]、 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 However, in either case, a monovalent organic radical having at least one (meth)acrylate group but no urethane group is independently selected from the group, R ＡＣ However, in either case, the group consists of monovalent organic radicals having at least one carboxylic acid ester group but lacking a (meth)acrylate group and a urethane group, and is independently selected from this group. The composition according to claim 8, characterized in that...

11. The composition according to claim 8, characterized in that the composition is curable.

12. A method for preparing the composition according to claim 8, (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 components (b) to (e) to the mixture of step (i), (iii) A step of removing component (f) from the mixture of step (ii), (iv) A step of preparing a mixture by optionally adding at least one of the components (b) to (e) to the mixture of step (iii) if the component was not added in step (ii). A method including or consisting of the following.

13. A peelable coating that can be obtained by curing the composition according to claim 8.

14. A protective film that can be obtained by curing the composition according to claim 8.

15. A protective coating that can be obtained by curing the composition according to claim 8.

16. A 3D printed object that can be obtained by 3D printing of the composition according to claim 8.

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