Silicone urethane (METH) acrylates and their use in coating compositions

Abstract

The present invention relates to a composition comprising a silicone urethane (meth) acrylate having at least three (meth) acrylate groups and urethane groups that are not more than (meth) acrylate groups, to a method for preparing said composition, and to a barrier coating, a protective film and a protective coating obtainable by curing said composition.

Description

[0001] The present invention relates to a composition comprising a silicone urethane (meth)acrylate having at least three (meth)acrylate groups and no more urethane groups than (meth)acrylate groups, a method for preparing the composition, and release coatings, protective films and protective coatings obtainable by curing the composition.

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

[0003] KR 20170128955 A discloses silicone urethane (meth) acrylates as photocurable polymers for 3D printing. In Example 1, silicone urethane acrylate is prepared by reacting 1 mol of hydroxyl-terminated polydimethylsiloxane with 2 mol of hexamethylene diisocyanate (HDI) and then with 2 mol of hydroxyethyl acrylate (HEA). In Example 2, silicone urethane acrylate is prepared in the same manner by replacing HDI with isophorone diisocyanate (IPDI). These silicone urethane acrylates of Examples 1 and 2 have two acrylate groups and four urethane groups. In Example 3, silicone urethane methacrylate is prepared by reacting 1 mol of hydroxyl-terminated polydimethylsiloxane with 2 mol of 2-isocyanatoethyl methacrylate, which is a harmful and toxic compound. The polymer of Example 3 has two methacrylate groups and two urethane groups. It is also described that these photocurable polymers are flexible, have high photocuring speeds, and are easy to handle.

[0004] CN 106519182 A discloses silicone urethane acrylate for use in the field of release coatings. The silicone urethane acrylate is prepared by a method comprising the following steps:

[0005] (1) reacting an organosilicon diol with a diisocyanate in a molar ratio of hydroxyl group to isocyanate group of 1:2;

[0006] (2) Hydroxyethyl acrylate or hydroxyethyl methacrylate is reacted with the prepolymer obtained in step (1) at a molar ratio of hydroxyl group to isocyanate group of 1:1.

[0007] The organosilicon diol is a chain-type silicon diol having an organic group containing two hydroxyl groups at one of its chain ends. The diisocyanate is preferably selected from toluene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate. The obtained silicone urethane acrylate has two (meth)acrylate groups and four urethane groups.

[0008] CN109577077A relates to a method for preparing self-adhesive release paper by electron beam curing. The release paper comprises a base paper layer and an isolation coating, the latter being obtained by electron beam curing an isolation coating composition, the isolation coating composition containing 50 to 100 parts of silicone-modified urethane acrylate, 0 to 50 parts of silicone-modified polyacrylate and 10 to 20 parts of a reactive diluent.

[0009] However, silicone urethane (meth) acrylates known in the art as coating composition components generally show only moderate photocuring rates, or have high viscosity or even solids at room temperature, which makes them difficult to handle. In order to improve their processability, the treatment of silicone urethane (meth) acrylates is carried out at higher temperatures, or a larger amount of solvents or reactive diluents are added, which in turn leads to other disadvantages, such as increased energy consumption, additional method steps to remove solvents and / or possible adverse effects on the desired properties of the cured product. It is also preferred that the curing rate is high and the curing depth is increased to accelerate the treatment. In addition, preferably, the cured product is flexible and has good mechanical properties, such as high elongation at break. It is also preferred that the cured product is an elastic material, i.e., after deformation such as elongation, the product should return to its original shape. The surface of the cured product should be smooth and have good isolation properties. The surface of the cured product should also have good scratch resistance. It is also required to avoid highly toxic or highly dangerous compounds in the synthesis of silicone urethane (meth) acrylates.

[0010] Therefore, there is still a need to provide silicone urethane (meth)acrylates as components of coating compositions that are superior to the prior art, and compositions comprising the same. Therefore, the problem addressed by the present invention is to overcome at least one disadvantage of the prior art.

[0011] Surprisingly, it has been found that the subject matter of the independent claims overcomes at least one disadvantage of the prior art.

[0012] The objects of the invention are therefore achieved by the subject-matter of the independent claims. Preferred embodiments of the invention are specified in the dependent claims, the examples and the description.

[0013] According to a first aspect of the present invention, there is provided a composition comprising or consisting of the following components:

[0014] (a) at least one silicone urethane (meth)acrylate having

[0015] - at least three (meth)acrylate groups, and

[0016] - no more urethane groups than (meth)acrylate groups, preferably as many urethane groups as (meth)acrylate groups;

[0017] (b) at least one organic (meth)acrylate not having any silicon atoms;

[0018] (c) at least one silicone (meth)acrylate not having any urethane groups;

[0019] (d) optionally at least one curing catalyst;

[0020] (e) optionally at least one additive;

[0021] (f) optionally at least one solvent;

[0022] Features:

[0023] Based on the total weight of the sum of components (a) to (f) and / or based on the total weight of the composition, preferably based on the total weight of the composition, the composition contains

[0024] - 20 to 70% by weight, preferably 25 to 60% by weight, more preferably 25 to 50% by weight of component (a);

[0025] - 20 to 80% by weight, preferably 30 to 70% by weight, more preferably 40 to 65% by weight of component (b);

[0026] - 1 to 60% by weight, preferably 2 to 40% by weight, more preferably 5 to 25% by weight of at least component (c);

[0027] - 0 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.5 to 2.5% by weight of component (d);

[0028] - 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 0 to 5% by weight of component (e);

[0029] - 0 to 10% by weight, preferably 0 to 5% by weight, more preferably 0 to 1% by weight of component (f).

[0030] According to a second aspect of the present invention, there is provided a method for preparing the composition, comprising or consisting of the following steps:

[0031] (i) preparing a mixture of component (a) and component (f);

[0032] (ii) preparing a mixture by adding at least one of components (b) to (e), preferably components (b) and / or (c), to the mixture of step (i);

[0033] (iii) (substantially) removing component (f) from the mixture of step (ii);

[0034] (iv) Optionally, if at least one of components (b) to (e) is not added in step (ii), a mixture is prepared by adding at least one of components (b) to (e) to the mixture of step (iii).

[0035] According to a third aspect of the present invention, there is provided a method for preparing an isolation coating, a protective film or a protective coating, which preferably comprises the following indirect or direct successive steps:

[0036] a. applying the composition to a surface;

[0037] b. Curing the composition, preferably by irradiation with UV radiation.

[0038] According to a fourth aspect of the present invention, there is provided a barrier coating, a protective film or a protective coating obtainable by curing the composition, preferably obtainable by the method.

[0039] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context dictates otherwise.

[0040] The term "comprising" is synonymous with "including", "containing", and is inclusive or open-ended and does not exclude additional unrecited members, elements or method steps.

[0041] When amounts, concentrations, sizes and other parameters are expressed in the form of ranges, preferred ranges, upper values, lower values, or both, 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.

[0042] Unless otherwise stated, when a numerical range of the form "from X to Y" is reported below, where X and Y represent the limits of the numerical range, this is synonymous with the expression "from at least X up to and including Y". Therefore, unless otherwise stated, the expression of a range includes the range limits X and Y.

[0043] The words "preferred" and "preferably" are often used herein to refer to embodiments of the present disclosure that may provide specific benefits under certain circumstances. However, the recitation of one or more preferred embodiments does not mean that other embodiments are not useful, and is not intended to exclude those other embodiments from the scope of the present disclosure.

[0044] When measured values, parameters or material properties determined by measurements are reported below, these are measured values, parameters or material properties at 25° C. and preferably at a pressure of 101 325 Pa (standard pressure), unless otherwise stated.

[0045] As used herein, room temperature (RT) is 23°C ± 2°C.

[0046] The expression "(meth)acrylic" means "methacrylic" and / or "acrylic". Thus, the expression "(meth)acrylate" means "methacrylate" and / or "acrylate". As used herein, "acrylate" means "ester of acrylic acid", and "methacrylate" means "ester of methacrylic acid".

[0047] In the context of the present invention, silicone urethane (meth)acrylate is understood to mean an organosiloxane containing urethane groups and carrying methacrylate groups and / or acrylate groups (hereinafter also referred to as (meth)acrylate groups). Organosiloxanes are also referred to hereinafter as siloxanes for short.

[0048] Organosiloxanes are understood to mean compounds having organic groups bonded to silicon atoms and structural units of the formula ≡Si-O-Si≡, where "≡" represents the three remaining valencies of the silicon atom in question. Organosiloxanes are preferably selected from M=[R3SiO 1 / 2 ]、D=[R2SiO 2 / 2 ]、T=[RSiO 3 / 2 ] and optionally also has the formula Q=[SiO 4 / 2 ] unit, wherein R is a monovalent organic group. The groups R can be selected independently of each other and are the same or different when compared in pairs. The groups R can also be partially substituted by non-organic monovalent groups such as hydroxyl or chlorine. The references cited in connection with the M, D, T, Q nomenclature used herein to describe the structural units of organosiloxanes are W. Noll, Chemie und Technologie der Silicone [Chemistry and Technology of the Silicones], Verlag Chemie GmbH, Weinheim (1960), pages 2 and thereafter.

[0049] The various repeating units in the following formulae (C), (F), (Q) and (S) may be statistically distributed. The statistical distribution may have a block structure with any number of blocks and in any order, or they may obey a random distribution; they may also have an alternating structure, or, if any, form a gradient along the chain; in particular, they may also form any mixed form thereof, wherein groups of different distributions may optionally follow one another. Specific embodiments may be defined below, wherein features such as indices or structural components or ranges or statistical distributions are subject to restrictions of the embodiment. All other features not affected by the restrictions remain unchanged.

[0050] In case molecules / molecular fragments have one or more stereogenic centers (chiral centers) or can differentiate into isomers due to symmetry or due to other effects such as hindered rotation, the invention includes all possible isomers.

[0051] Unless otherwise specified, molecular weights given herein are number average molecular weight (M n ). All molecular weight data refer to the values ​​obtained by gel permeation chromatography (GPC) as described in the examples.

[0052] When documents are cited within the context of the present description, their entire content is intended to become part of the disclosure of the present invention.

[0053] In a first aspect of the present invention, there is provided a composition comprising or (essentially) consisting of the following components:

[0054] (a) at least one silicone urethane (meth)acrylate having

[0055] - at least three (meth)acrylate groups, and

[0056] - no more urethane groups than (meth)acrylate groups, preferably as many urethane groups as (meth)acrylate groups;

[0057] (b) at least one organic (meth)acrylate not having any silicon atoms;

[0058] (c) at least one silicone (meth)acrylate not having any urethane groups;

[0059] (d) optionally at least one curing catalyst;

[0060] (e) optionally at least one additive;

[0061] (f) optionally at least one solvent;

[0062] Features:

[0063] Based on the total weight of the sum of components (a) to (f) and / or based on the total weight of the composition, preferably based on the total weight of the composition, the composition contains

[0064] - 20 to 70% by weight, preferably 25 to 60% by weight, more preferably 25 to 50% by weight of component (a);

[0065] - 20 to 80% by weight, preferably 30 to 70% by weight, more preferably 40 to 65% by weight of component (b);

[0066] - 1 to 60% by weight, preferably 2 to 40% by weight, more preferably 5 to 25% by weight of at least component (c);

[0067] - 0 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.5 to 2.5% by weight of component (d);

[0068] - 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 0 to 5% by weight of component (e);

[0069] - 0 to 10% by weight, preferably 0 to 5% by weight, more preferably 0 to 1% by weight of component (f).

[0070] Silicone urethane (meth)acrylate has

[0071] - at least three (meth)acrylate groups, and

[0072] No more urethane groups than (meth)acrylate groups, preferably as many urethane groups as (meth)acrylate groups.

[0073] Preferably, the silicone urethane (meth)acrylate has m (meth)acrylate groups and n urethane groups, wherein

[0074] m is an integer of at least 3, preferably 3 to 5, more preferably 4;

[0075] n is an integer of at least 2, preferably 2 to 4, more preferably 4;

[0076] The condition is m≥n, preferably m=n.

[0077] Examples of possible combinations (m; n) of m (meth)acrylate groups and n urethane groups include, but are not limited to, (3; 1), (3; 2), (3; 3), (4; 1), (4; 2), (4; 3), (4; 4), (5; 1), (5; 2), (5; 3), (5; 4), (5; 5); (6; 1), (6; 2), (6; 3), (6; 4), (6; 5) or (6; 6); preferably (3; 2), (3; 3), (4; 2), (4; 3), (4; 4), (5; 2), (5; 3), (5; 4) or (5; 5), particularly preferably (4; 4).

[0078] Preferably, the silicone urethane (meth)acrylate is represented by formula (B),

[0079] X(-Y) p Formula (B),

[0080] in

[0081] X is a p-valent silicone group;

[0082] Y is bonded to the silicon atom of the silicone group, and

[0083] are independently selected in each case from monovalent organic groups having at least one urethane group and at least one (meth)acrylate group,

[0084] is preferably independently selected in each case from monovalent organic groups having two (meth)acrylate groups and one or two urethane groups,

[0085] More preferably, they are each independently selected from the group consisting of

[0086] and a monovalent organic group having two carbamate groups;

[0087] p is an integer of at least 1, preferably 2 to 4, more preferably 2.

[0088] The silicone group may be linear, branched, cyclic or a combination thereof. Preferably, the silicone group is linear. Particularly preferably, the silicone group is a divalent polydimethylsiloxane group.

[0089] Preferably, the silicone urethane (meth)acrylate comprises a unit represented by formula (C),

[0090] [R a Y b SiO (4-a-b) / 2 ] formula (C),

[0091] in

[0092] a is an integer from 0 to 2, preferably 1 or 2;

[0093] b is an integer from 1 to 3, preferably 1;

[0094] The condition is that a+b is 1 to 3;

[0095] R is independently selected in each case from monovalent organic groups without any carbamate groups,

[0096] is preferably independently selected at each occurrence from monovalent hydrocarbon radicals having 1 to 30 carbon atoms,

[0097] More preferably, it is methyl;

[0098] Y is as defined above.

[0099] Preferably, the silicone urethane (meth)acrylate has exactly two units of formula (C) as defined above, and particularly preferably each of these units carries two radicals R and one radical Y, ie particularly preferably a=2 and b=1.

[0100] Preferably, the silicone urethane (meth)acrylate comprises a group of formula (A), preferably contained in the group Y:

[0101]

[0102] in

[0103] Z 1 is independently selected at each occurrence from -CH3 and -H, preferably -H;

[0104] Z 2 is a divalent organic group, preferably an alkylene group, preferably derived from OCN-Z 2 -Alkylene of isophorone diisocyanate of diisocyanate of CNO;

[0105] Z 3 is a (q+1)-valent organic group, wherein q is an integer of 1 to 3, preferably an alkylene group, preferably -(C2H4)-;

[0106] Z 4 is independently selected at each occurrence from -CH3 and -H, preferably -H;

[0107] And wherein each dashed line represents a covalent bond.

[0108] Examples of covalent bonds represented by dashed lines are bonds to hydrogen groups or to organic groups such as alkyl or alkylene groups, which may be linear, branched or cyclic and optionally interrupted by oxygen atoms. Preferably, at least one of the dashed lines represents a covalent bond to an organic group which itself has a covalent bond to a silicon atom, wherein the organic group is preferably a divalent hydrocarbon group which may be interrupted by oxygen atoms.

[0109] Preferably, Z 2 Z is independently selected at each occurrence from divalent, saturated or unsaturated, linear or branched or cyclic hydrocarbon radicals having 1 to 30 carbon atoms. 2 Can be OCN-Z 2 -CNO (formula (D)) residue of a diisocyanate. The term "residue of a diisocyanate" is defined herein as the molecular structure of a diisocyanate from which all isocyanate groups have been removed. Examples of suitable diisocyanates are given below. Particularly preferably, Z 2 It is derived from the formula OCN-Z 2 - a divalent radical of a diisocyanate of CNO, wherein the diisocyanate is IPDI.

[0110] Preferably, Z 3 Z is independently selected at each occurrence from a (q+1)-valent saturated or unsaturated, linear or branched or cyclic hydrocarbon radical having 2 to 30 carbon atoms. 3 may be the residue of a hydroxy-functional (meth)acrylate of formula (E),

[0111]

[0112]

[0113] Examples of suitable hydroxy-functional (meth)acrylates are given below. Hydroxyethyl acrylate is particularly preferred.

[0114] Preferably, the silicone urethane (meth)acrylate is represented by formula (F),

[0115] M m1 M UA m2 M A m3 D d1 D UA d2 D A d3 T t Q q Formula (F),

[0116] in

[0117] M=[R3SiO1 / 2 ];

[0118] M UA =[R2(R UA )SiO 1 / 2 ];

[0119] M A =[R2(R A )SiO 1 / 2 ];

[0120] D=[R2SiO 2 / 2 ];

[0121] D UA =[R(R UA )SiO 2 / 2 ];

[0122] D A =[R(R A )SiO 2 / 2 ];

[0123] T=[RSiO 3 / 2 ];

[0124] Q=[SiO 4 / 2 ];

[0125] m1 is an integer from 0 to 32, preferably from 0 to 22, more preferably 0;

[0126] m2 is an integer from 0 to 32, preferably from 1 to 10, more preferably 2;

[0127] m3 is an integer from 0 to 32, preferably from 0 to 22, more preferably 0;

[0128] d1 is an integer from 1 to 1000, preferably from 5 to 500, more preferably from 10 to 400;

[0129] d2 is an integer from 0 to 10, preferably from 0 to 5, more preferably 0;

[0130] d3 is an integer from 0 to 10, preferably from 0 to 5, more preferably 0;

[0131] t is an integer from 0 to 10, preferably from 0 to 5, more preferably from 1 to 5;

[0132] q is an integer from 0 to 10, preferably from 0 to 5, more preferably from 1 to 5;

[0133] The conditions are:

[0134] m1+m2+m3 is at least 2, preferably 2 to 20, more preferably 2 to 10;

[0135] m2+d2 is at least 1, preferably 2 to 10, more preferably 2 to 6;

[0136] in

[0137] R is independently selected in each case from monovalent organic groups without any urethane groups or (meth)acrylate groups,

[0138] is preferably independently selected at each occurrence from monovalent hydrocarbon radicals having 1 to 30 carbon atoms,

[0139] More preferably, it is methyl;

[0140] R UA are independently selected in each case from monovalent organic groups having at least one (meth)acrylate group and at least one urethane group,

[0141] is preferably independently selected in each case from monovalent organic groups having two (meth)acrylate groups and one or two urethane groups,

[0142] More preferably, each occurrence is independently selected from the monovalent organic groups represented by formula (G),

[0143]

[0144] x1 is an integer from 1 to 3, preferably 3;

[0145] R 1 is independently selected at each occurrence from a hydrogen radical, a monovalent hydrocarbon radical having 1 to 6 carbon atoms, 2 and R 3 ;

[0146] is preferably independently selected at each occurrence from a hydrogen radical and a monovalent hydrocarbon radical having 1 to 6 carbon atoms;

[0147] More preferably, it is a hydrogen group;

[0148] R 2 is independently selected at each occurrence from a hydrogen group, an R 3 and a monovalent organic group having at least one (meth)acrylate group;

[0149] Preferably, each occurrence is independently selected from R 3 and a monovalent organic group having at least one (meth)acrylate group;

[0150] More preferably, each occurrence is independently selected from monovalent groups of formula (H)

[0151]

[0152] x2=(1-x3);

[0153] R3 are independently selected in each case from monovalent organic groups having at least one urethane group and at least one (meth)acrylate group;

[0154] are preferably independently selected in each case from monovalent organic groups having exactly two urethane groups and exactly one (meth)acrylate group;

[0155] More preferably, each occurrence is independently selected from monovalent organic groups of formula (I),

[0156]

[0157] x3 is an integer selected from 0 or 1, preferably 0;

[0158] R 4 is independently selected at each occurrence from a hydrogen group or a methyl group, preferably a hydrogen group;

[0159] R 5 is independently selected in each case from a divalent, saturated or unsaturated, linear or branched or cyclic hydrocarbon radical having 1 to 30 carbon atoms;

[0160] Preferably it is a divalent group of formula (J),

[0161]

[0162] R A are independently in each case selected from monovalent organic groups having at least one (meth)acrylate group but no urethane group;

[0163] Preferably, each occurrence is independently selected from monovalent groups represented by formula (K) or (L);

[0164] More preferably, each occurrence is independently selected from the monovalent groups represented by formula (K);

[0165]

[0166] where x1 and R 4 As defined above.

[0167] More preferably, the group R UA or Y is represented by at least one of the formulas (M), (N), (O) and (P), respectively:

[0168]

[0169] Preferably, the following apply to the silicone urethane (meth)acrylate according to formula (F): m1=d2=t=q=0;

[0170] m2 = 2; and

[0171] d1 is 1 to 1000, preferably 5 to 500, more preferably 10 to 400, still more preferably 20 to 100.

[0172] Preferably, the (meth)acrylate groups of the silicone urethane (meth)acrylate are acrylate groups.

[0173] Preferably, the silicone urethane (meth)acrylates of the present invention do not contain groups containing moieties of the formula -(C=O)-NH- other than urethane groups.

[0174] Preferably, the silicone urethane (meth)acrylate has a viscosity at 25° C. of less than 200 Pa·s, preferably 0.5 to 150 Pa·s, more preferably 10 to 100 Pa·s. The glass transition temperature is preferably determined as described in the examples.

[0175] Preferably, the weight average molecular weight M of silicone urethane (meth)acrylate is w The weight average molecular weight is preferably determined as described in the examples.

[0176] Preferably, the number average molecular weight M of silicone urethane (meth)acrylate is n The weight average molecular weight is preferably determined as described in the examples.

[0177] Preferably, the glass transition temperature (T g ) below 100° C., preferably 20 to 80° C., more preferably 40 to 70° C. The glass transition temperature is preferably determined by differential scanning calorimetry (DSC) according to DSC method DIN 53765 at a heating rate of 10 K / min.

[0178] The preparation method of silicone urethane (meth) acrylate may comprise or consist of the following steps:

[0179] (1) reacting at least one hydroxy-functional silicone (meth)acrylate and at least one diisocyanate under conditions to form at least one urethane group to obtain an isocyanate-functional prepolymer;

[0180] (2) reacting at least one hydroxy-functional (meth)acrylate with the isocyanate-functional prepolymer obtained in step (1) under conditions to form at least one urethane bond.

[0181] Those skilled in the art know how to carry out the reaction and select suitable reaction conditions to achieve high yields, as described, for example, in KR 20170128955 A and CN 106519182 A. For example, preferably, the molar ratio of hydroxyl groups to isocyanate groups is about 1:2 in step (1) and about 1:1 in step (2).

[0182] Surprisingly, an alternative method for producing silicone urethane (meth) acrylates is more advantageous. According to this method, hydroxy-functional silicone (meth) acrylates are reacted with isocyanate-functional urethane (meth) acrylates. By applying this method, the viscosity can be further reduced.

[0183] Thus, in a preferred method of preparing a silicone urethane (meth)acrylate, the silicone urethane (meth)acrylate is formed by reacting at least one hydroxyl functional silicone (meth)acrylate with at least one isocyanate functional urethane (meth)acrylate.

[0184] The reaction of hydroxy-functional silicone (meth) acrylates with isocyanate-functional urethane (meth) acrylates requires the reaction of free NCO groups with hydroxyl groups and has been frequently described (WO 2010 / 072439A1 and references cited therein). The reaction can be carried out with or without a solvent. It is usually carried out in a temperature range between 40°C and 80°C. The reaction usually takes 4 to 8 hours. It can advantageously be catalyzed by conventional catalysts known in urethane chemistry such as organometallic compounds and tertiary amines. Examples of suitable organometallic compounds are dibutyltin dilaurate (DBTL), dibutyltin dineodecanoate, zinc octoate and bismuth neodecanoate. Examples of suitable tertiary amines are triethylamine or diazabicyclooctane. Suitable reaction components include all conventional equipment, tanks, static mixers, extruders, etc., preferably components with mixing or stirring functions. The NCO / OH ratio is usually 2:1 to 1:2, preferably 1.5:1 to 1:1.5, more preferably 1:1. The reaction can be carried out in the presence of a solvent, preferably in the absence of a solvent. A suitable solvent is, for example, acetone. It may be advantageous to react in the presence of an antioxidant / polymerization inhibitor to avoid polymerization of the (meth)acrylate groups. The inhibitor may be added to the reaction mixture together with an isocyanate-functional urethane (meth)acrylate, which may react with the hydroxyl groups of a hydroxy-functional silicone (meth)acrylate. If a solvent is used, then preferably after the reaction is complete, preferably under vacuum, the solvent may be removed, or the solvent may be removed after the preparation of the composition according to the present invention.

[0185] Examples of hydroxy-functional silicone (meth)acrylates that can be used to prepare the silicone urethane (meth)acrylates of the present invention are also known to those skilled in the art. Preferably, the hydroxy-functional silicone (meth)acrylate is formed by reacting at least one epoxy-functional silicone with (meth)acrylic acid and / or at least one hydroxy-functional (meth)acrylate. Even more preferably, the hydroxy-functional silicone (meth)acrylate is formed by reacting at least one epoxy-functional silicone with methacrylic acid and / or acrylic acid, in particular acrylic acid. This is described in US 4,978,726 A and the references cited therein. Examples of suitable hydroxy-functional (meth)acrylates that can be used are the same as those that can be used to synthesize isocyanate-functional urethane (meth)acrylates as described below.

[0186] Examples of isocyanate-functional urethane (meth)acrylates that can be used to prepare the silicone urethane (meth)acrylates of the present invention are also known in the prior art and are described, for example, in WO 2010 / 072439 A1 and WO 2010 / 115644 A1. Commercially available isocyanate-functional urethane (meth)acrylates that can be used are, for example EP DC-1241 (available from Evonik Industries AG, Germany). Isocyanate-functional urethane (meth)acrylates can be prepared by reacting diisocyanates with hydroxy-functional (meth)acrylates with formation of urethane bonds, as described in WO 2010 / 072439 A1.

[0187] Preferred diisocyanates are aliphatic diisocyanates, cycloaliphatic diisocyanates and araliphatic (i.e. aromatically substituted aliphatic) diisocyanates, as described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol. 14 / 2, pp. 61 to 70 and in the article by W. Siefken in Justus Liebigs Annalen der Chemie 562, pp. 75 to 136, such as 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-dimethyl Octane, 1,12-dodecane diisocyanate, ω,ω'-diisocyanato dipropyl 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-naphthalene)-2,5 -methylene diisocyanate, decahydro-8-methyl-(1,4-naphthalene)-3,5-methylene diisocyanate, hexahydro-4,7-methylene indan-1,5-methylene diisocyanate, hexahydro-4,7-methylene indan-2,5-methylene diisocyanate, hexahydro-4,7-methylene indan-1,6-methylene diisocyanate, hexahydro-4,7-methylene indan-2,5-methylene diisocyanate diisocyanate, hexahydro-4,7-indane-1,5-ylidene diisocyanate, hexahydro-4,7-indane-2,5-ylidene diisocyanate, hexahydro-4,7-indane-1,6-ylidene diisocyanate, hexahydro-4,7-indane-2,6-ylidene diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, 4,4'-methylenedicyclohexyl diisocyanate (4,4'-H 12 MDI), 2,2'-methylene dicyclohexyl diisocyanate (2,2'-H 12 MDI), 2,4-methylene dicyclohexyl diisocyanate (2,4-H 12MDI) or a mixture, 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 mixtures of these compounds. Other suitable isocyanates are described in the above-mentioned article of Justus Liebigs Annalen der Chemie, page 122 et seq. Preference is also given to 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (NBDI) and / or 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (NBDI). Particular preference is given to using aliphatic and cycloaliphatic diisocyanates which are readily available industrially, such as IPDI, HDI and HDI. 12 MDI, and isomeric mixtures thereof, in particular IPDI. The diisocyanate is an embodiment of a diisocyanate of formula (D) as given above.

[0188] Preferred hydroxy-functional (meth) acrylates are all compounds that not only carry at least one methacrylate or acrylate functional group but also carry just one hydroxyl group. Other components can be aliphatic alkyl, alicyclic alkyl, aromatic alkyl or heterocyclic alkyl. Oligomers or polymers can also be imagined. Preferred products that are easily available are such as, for example, 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. Hydroxyethyl acrylate is particularly preferred. A mixture of two or more of these hydroxy-functional (meth) acrylates can also be used. The hydroxy-functional (meth) acrylate is an embodiment of the hydroxy-functional (meth) acrylate of formula (E) as given above.

[0189] The composition according to the invention comprises or consists (essentially) of the following components:

[0190] (a) at least one silicone urethane (meth)acrylate according to the invention and / or prepared by the process according to the invention,

[0191] (b) optionally at least one organic (meth)acrylate not having any silicon atoms;

[0192] (c) optionally at least one silicone (meth)acrylate not having any urethane groups;

[0193] (d) optionally at least one curing catalyst;

[0194] (e) optionally at least one additive;

[0195] (f) optionally at least one solvent.

[0196] The composition comprises or (essentially consists of):

[0197] - 20 to 70% by weight, preferably 25 to 60% by weight, more preferably 25 to 50% by weight of component (a);

[0198] - 20 to 80% by weight, preferably 30 to 70% by weight, more preferably 40 to 65% by weight of component (b);

[0199] - 1 to 60% by weight, preferably 2 to 40% by weight, more preferably 5 to 25% by weight of at least component (c);

[0200] - 0 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.5 to 2.5% by weight of component (d);

[0201] - 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 0 to 5% by weight of component (e);

[0202] - 0 to 10 wt. %, preferably 0 to 5 wt. %, more preferably 0 to 1 wt. % of component (f);

[0203] Based on the total weight of the sum of components (a) to (f) and / or based on the total weight of the composition, preferably based on the total weight of the composition.

[0204] The one or more silicone urethane (meth)acrylates according to the invention are also denoted herein as component (a).

[0205] Preferably, the silicone urethane (meth)acrylate (component (a)) is present in the composition of the present invention in an amount of 5 to 100% by weight, preferably 5 to 20% by weight, more preferably 10 to 20% 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.

[0206] Preferably, the composition according to the present invention also comprises component (b). Component (b) can be used as a reactive diluent to reduce and adjust the viscosity of the composition. Alternatively, component (b) can be used as a crosslinking agent. Component (b) of the composition consists of one or more organic (meth) acrylates that do not have any silicon atoms. Therefore, the organic (meth) acrylate does not contain silicon atoms. Preferably, the organic (meth) acrylate consists only of the elements carbon, hydrogen, oxygen and nitrogen. Also preferably, the organic (meth) acrylate has 2 to 6 (meth) acrylate groups. Such compounds are described in European Coatings Tech Files, Patrick et al. "Radiation Curing: Coatings and Printing Inks", 2008, Vincentz Network, Hanover, Germany.

[0207] Particularly preferred organic (meth) acrylates are disclosed in WO 2016 / 096595 A1 and WO 2018 / 001687 A1. Examples of organic (meth) acrylates may be selected from, but are not limited to, 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 glycerol triacrylate, polyethylene glycol diacrylate, and ethoxylated and / or propoxylated derivatives thereof.

[0208] Suitable organic (meth)acrylates are also commercially available under the following trade names: TMPTA (Allnex SA, Germany), OTA480 (propoxylated glyceryl triacrylate, Allnex SA, Germany), TPGDA (Allnex SA, Germany), DPGDA (Allnex SA, Germany), 892 (Allnex SA, Germany), 11(M w 700 g / mol polyethylene glycol 600 diacrylate, Allnex SA, Germany), 45 (Allnex SA, Germany), PETIA (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, Allnex SA, Germany), 150 (bisphenol A derivative diacrylate, Allnex SA, Germany), 605 (mixture of 80% bisphenol A diepoxy acrylate and 20% TPGDA, Allnex SA, Germany), 40 (ethoxylated and propoxylated (total 1.2 propylene oxide and 5 ethylene oxide units) pentaerythritol tetraacrylate, Allnex SA, Germany), TMPTA (BASF, Germany), M200 (HDDA, RahnAG, Germany), M220 (TPGDA, Rahn AG, Germany), 3130 (ethoxylated trimethylolpropane triacrylate (total 3 ethylene oxide units), Rahn AG, Germany), SR 415 (ethoxylated (total 20 ethylene oxide units) trimethylolpropane triacrylate, Sartomer, France), SR 489 (tridecyl acrylate, Sartomer, France).

[0209] Suitable organic (meth)acrylates are also available from Evonik Industries AG (Germany) The preferred compound is glycerol formal methacrylate ( GLYFOMA), diurethane dimethacrylate ( HEMA TMDI), butyl diglycol methacrylate ( BDGMA), polyethylene glycol 200 dimethacrylate ( PEG200DMA), trimethylolpropane methacrylate ( TMPTMA), tetrahydrofurfuryl methacrylate ( THFMA), isobornyl methacrylate ( TerraIBOMA), isobornyl acrylate ( IBOA), methacrylate of fatty alcohol having an average of 13.0 carbon atoms ( Terra C13-MA) ​​or methacrylate of a fatty alcohol having an average of 17.4 carbon atoms ( Terra C17.4-MA).

[0210] The composition of the present invention more preferably comprises isobornyl methacrylate ( TerraIBOMA), isobornyl acrylate ( IBOA), Lauryl Acrylate, 45. Organic (meth)acrylates of hexanediol diacrylate and trimethylolpropane triacrylate.

[0211] Preferably, the (meth)acrylate groups of the organic (meth)acrylate (component (b)) silicone (meth)acrylate are acrylate groups.

[0212] Also preferably, the (meth)acrylate groups of the organic (meth)acrylate (component (b)) silicone (meth)acrylate are (meth)acrylate groups.

[0213] Preferably, the amount of organic (meth)acrylate (component (b)) present in the composition of the present invention is 0 to 60% by weight, preferably 0 to 30% by weight, 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, preferably based on the total weight of the composition.

[0214] Preferably, the composition according to the invention comprises component (c). Component (c) consists of at least one silicone (meth)acrylate which does not have any urethane groups. Therefore, the silicone (meth)acrylate does not contain any urethane groups.

[0215] Preferably, the at least one silicone (meth)acrylate of component (c) is represented by formula (Q) and / or the at least one silicone (meth)acrylate of component (c) is represented by formula (S),

[0216] M A m1 D d1 Formula (Q);

[0217] in

[0218] M A =[R2(R A )SiO 1 / 2 ];

[0219] D=[R2SiO 2 / 2 ];

[0220] m1 is an integer of 2;

[0221] d1 is an integer from 1 to 10000, preferably from 50 to 5000, more preferably from 70 to 2000;

[0222] in

[0223] R is independently selected in each case from monovalent organic groups without any urethane groups or (meth)acrylate groups,

[0224] is preferably independently selected at each occurrence from monovalent hydrocarbon radicals having 1 to 30 carbon atoms,

[0225] More preferably, it is methyl;

[0226] R A are independently in each case selected from monovalent organic groups having at least one (meth)acrylate group but not one urethane group;

[0227] Preferably, each occurrence is independently selected from monovalent groups represented by the formula (R),

[0228]

[0229] x1 is as defined above;

[0230] x4 is an integer 0 or 1, preferably 0;

[0231] R 6 is independently selected at each occurrence from monovalent hydrocarbon groups having 1 to 6 carbon atoms;

[0232] Preferably ethyl;

[0233] R 7 are independently in each case selected from monovalent organic groups having at least one (meth)acrylate group but no urethane group;

[0234] is preferably independently selected at each occurrence from monovalent groups of formula (H) as defined above;

[0235] M m1 D d1 D A d2 D AC d3 Formula (S)

[0236] in

[0237] M=[R3SiO 1 / 2 ];

[0238] D=[R2SiO 2 / 2 ];

[0239] D A =[R(R A )SiO 2 / 2 ];

[0240] D AC =[R(R AC )SiO 2 / 2 ];

[0241] in:

[0242] R, m1 and d1 are as defined above for formula (Q);

[0243] d2 is an integer from 1 to 20, preferably from 2 to 10, more preferably from 3 to 8;

[0244] d3 is an integer from 0 to 3, preferably from 0 to 2, more preferably from 0 to 1;

[0245] R A are independently in each case selected from monovalent organic groups having at least one (meth)acrylate group but no urethane group;

[0246] Preferably, each occurrence is independently selected from monovalent groups represented by formula (K) or (L);

[0247] More preferably, each occurrence is independently selected from the monovalent groups represented by formula (K);

[0248]

[0249] where x1 and R 4 As defined above;

[0250] R AC are independently in each case selected from monovalent organic groups having at least one carboxylate group but having no (meth)acrylate groups and urethane groups;

[0251] Preferably, independently in each case, selected from monovalent groups represented by formula (T) or (U),

[0252]

[0253] where x1 is defined as above;

[0254] R 5 is independently selected at each occurrence from monovalent hydrocarbon groups having 1 to 22 carbon atoms;

[0255] Preferred is methyl.

[0256] The at least one silicone (meth) acrylate of component (c) represented by formula (Q) is denoted as component (c1) herein. The at least one silicone (meth) acrylate of component (c) represented by formula (S) is denoted as component (c2) herein. Therefore, component (c) consists of component (c1) and / or component (c2), wherein component (c1) consists of at least one silicone (meth) acrylate represented by formula (Q), and wherein component (c2) consists of at least one silicone (meth) acrylate represented by formula (S).

[0257] Examples of silicone (meth)acrylates according to formula (Q) (component (c1 )) are known to those skilled in the art and can be prepared as described, for example, in EP 0940422 A1.

[0258] Examples of silicone (meth)acrylates according to formula (S) (component (c2)) are also known to those skilled in the art and can be prepared as described, for example, in EP 3168273 A1 and WO 2017187030 A1.

[0259] Preferably, the silicone (meth)acrylate (component (c)) is present in the composition of the invention in an amount of 0 to 95% by weight, preferably 65 to 85% by weight, 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.

[0260] Particularly preferably, the silicone (meth)acrylate according to formula (Q) (component (c1)) is present in the composition of the invention in an amount of 0 to 95% by weight, preferably 65 to 85% by weight, more preferably 70 to 80% by weight, based on the total weight of the sum of components (a) to (e) and / or on the total weight of the composition, preferably based on the total weight of the composition.

[0261] Particularly preferably, the silicone (meth)acrylate according to formula (S) (component (c2)) is present in the composition of the invention in an amount of 0 to 95% by weight, preferably 65 to 85% by weight, more preferably 70 to 80% by weight, based on the total weight of the sum of components (a) to (e) and / or on the total weight of the composition, preferably based on the total weight of the composition.

[0262] Preferably, the (meth)acrylate group of the silicone (meth)acrylate (component (c1)) represented by formula (Q) is an acrylate group. Also preferably, the (meth)acrylate group of the silicone (meth)acrylate (component (c2)) represented by formula (S) is an acrylate group. More preferably, 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 both acrylate groups.

[0263] Particularly preferably, the (meth)acrylate groups of components (a), (b) and (c), such as components (c1) and (c2), are all acrylate groups.

[0264] It is also particularly preferred that the (meth)acrylate groups of components (a) and (c) (such as (c1) and (c2)) are both acrylate groups, and the (meth)acrylate groups of component (b) are (meth)acrylate groups.

[0265] Component (d) of the composition according to the invention consists of one or more curing catalysts. Preferably, the curing catalyst is a compound which generates reactive species such as free radicals, cations or anions, more preferably free radicals, when exposed to an external trigger such as actinic radiation, preferably UV light and / or visible light, or heat. Thus, the curing catalyst may be a catalyst for photocuring (photoinitiator) or a catalyst for thermal curing (thermal curing catalyst).

[0266] The presence of one or more thermal curing catalysts in the composition of the present invention may be advantageous. Thermal curing catalysts are compounds that generate reactive species such as free radicals, cations or anions when exposed to heat. Preferably, thermal curing accelerators include organic peroxides such as 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (e.g., LUPEROX ), dilauroyl peroxide (such as LUPEROX ), dibenzoyl peroxide (such as LUPEROX ) and bis(tert-butyldioxyisopropyl)benzene (e.g. VulCUP ). 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, and peroxyketals, dialkyl peroxides, peroxydicarbonates and peroxyesters. Examples of thermal curing catalysts also include inorganic peroxides, such as peroxodisulfates, including sodium persulfate (Na2S2O8), potassium persulfate (K2S2O8) and ammonium persulfate ((NH4)2S2O8). Examples of thermal curing catalysts also include azobisisobutyronitrile (AIBN).

[0267] It may be advantageous to have one or more photoinitiators present in the compositions of the present invention. A photoinitiator is a compound that generates reactive species such as free radicals, cations or anions when exposed to actinic radiation, preferably UV light or visible light, more preferably UV light. Any suitable photoinitiator may be present in the compositions of the present invention, including Norrish Type I and Norrish Type II photoinitiators, and including conventional UV photoinitiators, examples of which include, but are not limited to, acetophenones (e.g., diethoxyacetophenone), phosphine oxides such as diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide (PPO), Irgacure 369, and the like (see, e.g., U.S. Pat. No. 9,453,142 to 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) -phenyl phosphine oxide, which is available under the trade name 819 is obtained from IGM resins (formerly known as 819, available from BASF SE). Other photoinitiators that can be used in the composition of the present invention are available under the product names TPO (diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide) and TPO-L (ethyl (2,4,6-trimethylbenzoyl) phenyl phosphite) is obtained from IGM resins. Particularly preferred are Norrish type 1 photoinitiators, such as, for example, benzophenone, benzoin, α-hydroxyalkylphenone, acylphosphine oxide or derivatives thereof. Conventional photoinitiators are described, for example, in "A Compilation of Photoinitiators Commercially Available for UV Today" (K. Dietliker, SITA Technology Ltd., London 2002).

[0268] Preferably, the amount of curing catalyst (component (d)) present in the composition of the present invention is 0 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.5 to 2.5% by weight, based on the total weight of the 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.

[0269] Component (e) of the composition according to the invention consists of one or more additives.

[0270] Component (e) may include solid particles suspended or dispersed therein as additives. Depending on the final product manufactured, any suitable solid particles can be used. The particles can be metallic, organic / polymeric, inorganic, or composite materials, or mixtures thereof. The particles can be non-conductive, semi-conductive or conductive (including metals and non-metallic or polymer conductors); and the particles can be magnetic, ferromagnetic, paramagnetic or non-magnetic. The particles can have any suitable shape, including spherical, elliptical, cylindrical, etc. The particles can have any suitable size (e.g., an average diameter of 1nm to 200μm). The particles can contain active agents or detectable compounds, although these can also be dissolved / solubilized in the composition of the present invention. For example, magnetic or paramagnetic particles or nanoparticles can be used.

[0271] Also depending on the specific purpose of the product being manufactured, component (e) may contain pigments, dyes, active compounds, detectable compounds (eg fluorescent compounds, phosphorescent compounds) as additives.

[0272] Particularly preferably, component (e) comprises a non-reactive pigment or dye that absorbs light as an additive. Suitable examples of such light absorbers include, but are not limited to: (i) titanium dioxide (e.g., in an amount of 0.05 wt % or 0.1 wt % to 1 wt % or 5 wt %), (ii) carbon black (e.g., in an amount of 0.05 wt % or 0.1 wt % to 1 wt % or 5 wt %), and / or organic ultraviolet light absorbers (UV blockers) such as hydroxybenzophenone, hydroxybenzotriazole, oxalanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, thiophene, and / or benzotriazole ultraviolet light absorbers (e.g., Mayzo BLS1326) (e.g., in an amount of 0.001 wt % or 0.005 wt % to 1 wt %, 2 wt % or 4 wt %). Examples of suitable organic UV absorbers include, but are not limited to, those described in U.S. Pat. Nos. 3,213,058; 6,916,867; 7,157,586; and 7,695,643; the disclosures of which are incorporated herein by reference. Another example of a suitable organic UV absorber is 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (BBOT).

[0273] If the composition comprises component (d) containing a thermal curing catalyst, then preferably, component (e) is also present and comprises a curing accelerator for thermal curing. 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.

[0274] If the composition comprises a component (d) comprising a photoinitiator, then preferably, component (e) is also present and comprises 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-isothiourea p-toluenesulfinate, nitriles such as N,N-dimethyl-p-aminobenzonitrile, and phosphorus compounds such as sodium diethylthiophosphate.

[0275] Depending on the desired properties of the part or object to be manufactured, the composition according to the present invention may contain any suitable filler as an additive (component (e)). Thus, 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 rubbers; reactive and non-reactive thermoplastics (including, but not limited to, poly(etherimide), maleimide-styrene terpolymers, polyacrylates, polysulfones and polyethersulfones, etc.), inorganic fillers such as silicates (such as talc, clay, silica, mica), glass, carbon nanotubes, graphene, cellulose nanocrystals, etc., including all combinations of the foregoing. Suitable fillers include, but are not limited to, toughening agents, such as core-shell rubbers. 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 composition according to the present invention. Suitable silica functionalized with methacrylate groups may, for example, be obtained under the trade name 701, 711, R7200 and R 8200 is available from Evonik Industries AG (Germany). Preferably, the filler is present in the composition of the invention in an amount of 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 0 to 5% by weight, based on the total weight of the 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.

[0276] The composition according to the invention preferably comprises a polymerization inhibitor and / or an antioxidant as an additive (component (e)). By using a polymerization inhibitor and / or an antioxidant, polymerization of the composition during its preparation and / or its storage can be prevented. Suitable polymerization inhibitors are, for example, 2,6-di-tert-butyl-4-methylphenol, catechol, 4-methoxyphenol, 4-tert-butoxyphenol, 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-butylbenzene, 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-butylmercaptomethyl-2,6-di-tert-butylphenol, 4-hydroxy-3,5-di-tert-butylphenylmethanesulfonic acid distearyl ester, 2,5-dihydroxytoluene, 2,5-dihydroxy-1-tert-butylbenzene, 2,5-dihydroxy-1,4-di-tert-butylbenzene, 3,4-dihydroxy-1-tert-butylbenzene, 2,3-dimethyl-1,4-bis[3,4-dihydroxyphenyl]-butane, 2,2'-thiobis(4-tert-octylphenol), (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO), and TEMPO derivatives such as 4-hydroxy-TEMPO. A preferred polymerization inhibitor is 2,6-di-tert-butyl-4-methylphenol (BHT), which is available from Oxiris Chemicals SA under the trade name The polymerization inhibitor is preferably present in the composition of the invention in an amount of 0.001 to 1 wt. %, more preferably 0.01 to 0.5 wt. %, based on the total composition.

[0277] Preferably, the total amount of additives (component (e)) present in the composition of the invention is 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 0 to 5% by weight, based on the total weight of the sum of components (a) to (e) and / or on the total weight of the composition, preferably based on the total weight of the composition.

[0278] Component (f) of the composition according to the present invention is composed 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, preferably, the composition according to the present invention is substantially free of solvent. Therefore, preferably, 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, the amount of the solvent present in the composition of the present invention is 0 to 10 weight %, preferably 0 to 5 weight %, more preferably 0 to 1 weight %.

[0279] The composition according to the invention is preferably used for producing a barrier coating, a protective film or a protective coating by curing the composition.

[0280] Therefore, preferably, the composition is curable, preferably curable by free radical reaction, wherein the free radical reaction can be initiated by heat, by UV radiation and / or by electron beam. The composition according to the present invention can be three-dimensionally crosslinked by free radicals, and can be thermally cured in a very short time under the influence of high-energy radiation such as UV or electron beam, to form a mechanical and chemical resistant layer, which has predeterminable anti-sticking properties and adhesive properties in view of the suitable formulation of the composition according to the present invention. When the radiation used is UV radiation, crosslinking / curing is preferably carried out in the presence of a photoinitiator and / or a photosensitizer. Preferred Norrish 1 type photoinitiators are such as, for example, benzophenone, benzoin, α-hydroxyalkyl phenone, acylphosphine oxide or derivatives thereof. Conventional photoinitiators are described in, for example, "A Compilation of Photoinitiators Commercially available for UV today" (K. Dietliker, SITA Technology Ltd., London 2002). Preferred compositions according to the invention contain photoinitiators and / or photosensitizers in a mass proportion of 0.01% to 10%, especially 0.1% to 5%, based on the mass of the total composition. Photoinitiators and / or photosensitizers are preferably soluble in the composition according to the invention, more preferably soluble in a mass proportion of 0.01% to 10%, especially 0.1% to 5%, based on the mass of the total composition.

[0281] The composition according to the present invention can be prepared by any suitable method, for example by mixing component (a) with one or more of the optional components (b) to (f) in any order. The solvent (component (f)) is mainly used to reduce the viscosity of the composition and promote the mixing of the components. Component (f) promotes the manufacture of the composition and the application of the composition. However, it is generally preferred to provide a composition that is substantially free of solvent, i.e., substantially free of component (f). Therefore, it is preferred to (substantially) remove the solvent (component (f)) from the composition after the composition is prepared or at a certain moment during its preparation.

[0282] Therefore, another aspect of the present invention is a process for preparing a composition according to the present invention, comprising or consisting of the following steps:

[0283] (i) preparing a mixture of component (a) and component (f);

[0284] (ii) preparing a mixture by adding at least one of components (b) to (e), preferably components (b) and / or (c), to the mixture of step (i);

[0285] (iii) (substantially) removing component (f) from the mixture of step (ii);

[0286] (iv) Optionally, if at least one of components (b) to (e) is not added in step (ii), a mixture is prepared by adding at least one of components (b) to (e) to the mixture of step (iii).

[0287] The process steps (i) to (iv) are carried out in the order given. However, they may be interrupted by additional intermediate process 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 accomplished at room temperature or at elevated temperature. Mixing may be accomplished by using conventional mixing devices such as high-speed mixers.

[0288] The composition according to the present invention can be used in various fields. The composition is particularly suitable for producing barrier coatings, protective films and protective coatings.

[0289] Another aspect of the present invention is therefore a barrier coating, protective film or protective coating obtainable by curing the composition according to the invention.

[0290] The composition according to the invention is preferably used to produce a release coating. Release coatings (also commonly referred to as anti-adhesive coatings) are known in the prior art. They are used in a variety of different ways for the production of labels, tapes or hygiene products. Release coatings are characterized by low adhesion when in contact with adhesives and consist of radiation-cured silicones. For the curing of functional silicones, two mechanisms are generally used. In the case of cationic curing, epoxy-functional organosiloxanes are polymerized by means of photoinitiators, which release acid when irradiated. In the case of free radical curing, silicone (meth) acrylates are polymerized by means of photoinitiators, which form free radicals when irradiated.

[0291] The compositions of the invention exhibit low viscosity, a highly rapid photocuring reaction and good mechanical properties, in particular with regard to tensile strength at break and elongation at break.

[0292] An advantage of the compositions used in the present invention is that they can be processed at room temperature below 50° C., preferably at or below 25° C. This is because the viscosity of the composition at the processing temperature is preferably below 20 Pa·s.

[0293] An advantage of the compositions used in the present invention is that they can be processed in the absence of solvents. Thus, no organic volatiles are generated during the additive manufacturing process.

[0294] The compositions used according to the invention have the further advantage that they can be produced in a simple manner.

[0295] An advantage of the compositions used in the present invention is that they can contain fillers, which lead to better characteristics, especially better tensile strength at break and elongation at break.

[0296] An advantage of the compositions used in the present invention is that they can contain fillers, which lead to better characteristics, especially good scratch resistance and good demoulding properties.

[0297] The compositions used in the present invention are further advantageous in that they comprise g By using these compositions, elastomers or products having one or more typical properties of elastomers (such as an elongation at break preferably greater than 40%, more preferably greater than 60%, most preferably greater than 100%) can be obtained through added manufacturing.

[0298] Another aspect of the present invention is a method for preparing a barrier coating, a protective film or a protective coating, which preferably comprises the following steps, which are carried out indirectly or directly in succession:

[0299] a. applying the composition to a surface;

[0300] b. Curing the composition, preferably by irradiating with UV radiation.

[0301] Therefore, preferably, a barrier coating, a protective film or a protective coating can be obtained by this method.

[0302] Suitable UV radiation sources for curing the compositions according to the invention are optionally doped medium-pressure mercury vapor lamps, or low-pressure mercury vapor lamps, UV-LED lamps or so-called excimer emitters. The UV emitters may be polychromatic or monochromatic. The emission range of the emitters is preferably within the absorption range of the photoinitiator and / or photosensitizer.

[0303] In the production of the barrier coating, preferably, the surface is the surface of a support, preferably the surface of a sheet-like support. The composition of the invention can be applied to the sheet-like support on one side or both sides. The sheet-like support is preferably selected from paper, fabric, metal foil and polymer film. The support can be smooth or can have a surface structure. Particularly preferred supports are polypropylene films and polyethylene films.

[0304] Release coatings can be applied, for example, to adhesive tapes, labels, packaging for self-adhesive hygiene products, food packaging, self-adhesive thermal paper or the lining of bituminous roofing membranes. Release coatings have a good release effect on the adhesive materials used in these applications.

[0305] The release effect of adhesive materials, usually tapes or labels in industrial applications, is expressed by the release force, with a low release force indicating a good release effect. The release force is determined according to the FINAT manual 8th edition, The Hague / NL, 2009, named FTM 10, modified in that the storage is carried out at 40°C under pressure. The release force depends on the quality of the release coating (e.g. uniformity, thickness and / or smoothness of the coating), the adhesive material or adhesives, and the test conditions. Therefore, for the evaluation of the release coating, the adhesive or adhesive materials present and the test conditions should be the same. A 2.5 cm wide tape is used. The isolation force was determined using Tesa 7475 (trademark, Tesa SE, Hamburg, Germany).

[0306] The barrier coating of the invention preferably has a barrier force of at most 20 cN / 2.5 cm, more preferably at most 10 cN / 2.5 cm, very preferably at most 8 cN / 2.5 cm, and a barrier force of at least 0.5 cN / 2.5 cm, preferably at least 1 cN / 2.5 cm.

[0307] Even without further elaboration, it is believed that one skilled in the art will be able to utilize the above description to the broadest extent. Therefore, the preferred embodiments and examples are to be construed as merely descriptive disclosures which are not limiting in any way.

[0308] All definitions, embodiments and descriptions applicable to one aspect of the invention also apply mutatis mutandis to the other aspects of the invention, and vice versa.

[0309] refer to Figure 1 The subject matter of the present invention is described more specifically without intending to limit the subject matter of the present invention thereto.

[0310] Figure 1 A reaction route for synthesizing a silicone urethane (meth)acrylate (7) according to formula (A) is shown, which is formed by reacting a hydroxyl-functional silicone (meth)acrylate (5) and an isocyanate-functional urethane (meth)acrylate (6), wherein the hydroxyl-functional silicone (meth)acrylate (5) is formed by reacting (meth)acrylic acid (1) and an epoxy-functional silicone (2), and wherein the isocyanate-functional urethane (meth)acrylate (6) is formed by reacting a diisocyanate (3) of formula (D) and a hydroxyl-functional (meth)acrylate (4) of formula (E). Example

[0311] The following examples are only intended to illustrate the present invention to those skilled in the art and do not constitute any limitation to the claimed subject matter.

[0312] method

[0313] Epoxy value:

[0314] The epoxy value is determined in % by weight according to DIN EN ISO 3001 (1999-11) and ASTM D 1652 (2011).

[0315] Viscosity:

[0316] The viscosity is measured with a Brookfield R / S-CPS Plus rheometer using an RP75 measuring plate at 25° C. The test method is described in DIN 53019 (DIN 53019-1 (2008-09), DIN 53019-2 (2001-02) and DIN 53019-3 (2008-09)).

[0317] Acid value:

[0318] The acid number is determined in mg KOH / g polymer by titration in accordance with DIN EN ISO 2114 (2002-06).

[0319] Hydroxyl value (OH value):

[0320] The OH number is determined by titration in mg KOH / g polymer according to DIN EN ISO 4629-2 (2016-12).

[0321] Isocyanate value (NCO value):

[0322] The NCO value is determined in % by weight by titration in accordance with DIN EN 1242 (2013-05).

[0323] Gel Permeation Chromatography (GPC):

[0324] Weight average molecular weight M w and number average molecular weight M n The GPC measurements were performed under the following measurement conditions: column combination SDV1000 / (length 55 cm), temperature 35° C., THF as mobile phase, flow rate 0.35 ml / min, sample concentration 10 g / l, RI detector, polymers were evaluated relative to polystyrene standards (162-2520 000 g / mol).

[0325] Material

[0326] AT EP-DC 1241:

[0327] AT EP-DC 1241 (Evonik Industries AG) is a commercially available adduct of 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate, HEA) and 5-isocyanato-(isocyanatomethyl)-1,3,3-trimethylcyclohexane (isophorone diisocyanate, IPDI), which contains the following isomers:

[0328]

[0329] Component (a) - Silicone urethane (meth)acrylate according to formula (F)

[0330] synthesis

[0331] S1) preparing a silicone urethane acrylate according to formula (F) wherein 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), R4 =H, and R 5 =Formula (J).

[0332] Into a 2L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 94.4g of acrylic acid, 0.3g of methylhydroquinone, 69.5g of n-butanol, 41.7g of methyl isobutyl ketone and 3g of a 50% aqueous solution of chromium (III) acetate were charged and stirred. Heat to 115°C and simultaneously add 1291g of polydimethylsiloxane modified with terminal epoxy groups and having an epoxy value of 1.32% by weight. Stirring was continued at 115°C-120°C until the conversion of epoxy groups as determined by the acid value was >99%. All volatiles were then distilled off at 120°C and full vacuum. Filtration gave a liquid silicone acrylate having a viscosity of <200mPa·s at 25°C and a hydroxyl value of 52mg KOH / g.

[0333] In a 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 1078.8 g of the silicone acrylate thus prepared was mixed with 356.2 g of EP-DC 1241 and 2.87 g of TIB KAT 716LA were mixed and stirred at 60° C. for 6 hours. The residual NCO content of the high-viscosity silicone urethane acrylate was <0.03%, and the number average molecular weight M was determined by GPC. n is 4395 g / mol, and the weight average molecular weight M w It is 6513g / mol.

[0334] S2) preparing a silicone urethane acrylate according to formula (F) wherein m1=0, m2=1, m3=1, d1=28, d2=t=q=0, x1=3, (x2=1 and x3=0) or (x2=1 and x3=0), R=CH3, R 1 =H, R 2 = Formula (H), R 3 = Formula (I), R 4 =H, R 5 = Formula (J), and R A =Formula (K) or (L).

[0335] In a 2L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 253 g of silicone acrylate prepared according to Example S1 and having a hydroxyl value of 51 mg KOH / g was mixed with 40.96 g of EP-DC 1241 and 0.59 g of TIB KAT 716LA were mixed and stirred at 60°C for 6 hours. The viscosity of the obtained silicone urethane acrylate at 25°C was 1837 mPa·s, and the number average molecular weight M determined by GPC was nis 2872 g / mol, and the weight average molecular weight M w It is 5377g / mol.

[0336] S3) preparing a silicone urethane acrylate according to formula (F) wherein 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).

[0337] A 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer was charged 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 EP 3168273 A1 and 1.7 g of a 50% aqueous solution of chromium(III) acetate, while stirring. Heating to 115° C., 2763.5 g of a polydimethylsiloxane modified with terminal epoxy groups and having an epoxy number of 0.92% by weight was added. Stirring was continued at 115° C.-120° C. until the conversion of the epoxy groups, as determined by the acid number, was >99%. All volatiles were then distilled off at 120° C. and 3 mbar vacuum by slight degassing. Filtration gave a liquid silicone acrylate having a hydroxyl number of 30 mg KOH / g.

[0338] In a 2L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 3140.8 g of the silicone acrylate thus prepared was mixed with 1123.5 g of acetone, 604.2 g of EP-DC 1241 and 7.5 g of TIB KAT716LA were mixed and stirred at 60° C. for 6 hours. A green-brown transparent product was obtained by distillation at 60° C. and 3 mbar with a small amount of gas release, and its viscosity at 25° C. was 18216 mPa·s.

[0339] S4) preparing a silicone urethane acrylate according to formula (F) wherein m1=0, m2=2, m3=0, d1=8, d2=d3=t=q=0, x1=3, x3=1, R=CH3, R 1 =C2H5, R 2 =R 3 = Formula (I), R 4 =H, and R 5 =Formula (J).

[0340] A 5 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer was charged with 47.7 g of a hydroxyl-functional siloxane having a hydroxyl value of 200 mg KOH / g prepared according to Example 1 of EP 0940422 B and 57.7 g of EP-DC 1241, and the mixture was heated to 80°C while stirring. 0.21 g KAT716LA was added and the mixture was stirred at 80°C for 5 hours. During this period, the viscosity increased sharply. This gave a transparent yellow polymer which was highly viscous at 80°C and solidified into a glassy substance at room temperature.

[0341] S5) preparing a silicone urethane acrylate according to formula (F) wherein m1=0, m2=2, m3=0, d1=78, d2=d3=t=q=0, x1=3, x3=1, R=CH3, R 1 =C2H5, R 2 =R 3 = Formula (I), R 4 =H, and R 5 =Formula (J).

[0342] In a 5L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 1055.21 g of a hydroxyl-functional siloxane having a hydroxyl value of 42 mg KOH / g prepared according to the prior art disclosed in EP 0940422 B1 and 281.41 g of EP-DC 1241 was dissolved in 2004.94 g toluene and 2.67 g KAT 716LA.

[0343] The reaction mixture was heated to 60° C. and stirred for 4 h. After distilling off the toluene at 70° C. and reaching the target pressure of 20 mbar after 2 h, a polymer was obtained which was very viscous at 70° C. and solidified into a glassy substance at room temperature. The number average molecular weight M determined by GPC n is 8638 g / mol, and the weight average molecular weight M w It is 28 731 g / mol.

[0344] S6) preparing a silicone urethane acrylate according to formula (F) wherein m1=0, m2=2, m3=0, d1=48, d2=d3=t=q=0, x1=3, x3=0, R=CH3, R 1 =R 2 =H, R 3 = Formula (I), R 4 =H, and R 5 =Formula (J).

[0345] A 0.5 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer was charged with 179.0 g of polydimethylsiloxane modified with terminal hydroxyl groups and having a hydroxyl value of 47 mg KOH / g, and 53.3 g of EP DC1241 and 116.1 g toluene were stirred at the same time. 0.23 g KAT 716LA. The reaction mixture was heated to 60° C. and stirred at 60° C. for 4 hours. The solvent was then distilled off on a rotary evaporator at 80° C. and 2 mbar over the course of one hour. A very viscous polymer was obtained which solidified at room temperature.

[0346] S7) preparing a silicone urethane acrylate according to formula (F), wherein 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).

[0347] A 0.5 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer was charged 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 EP 3168273 A1 and 0.19 g of a 50% aqueous solution of chromium(III) acetate, while stirring. Heating to 120° C., 303.7 g of a linear polydimethylsiloxane modified with one terminal epoxy group and one terminal trimethylsiloxy group and having an epoxy number of 0.79% by weight was added. Stirring was continued at 115° C.-120° C. until the conversion of the epoxy groups, as determined by the acid number, was >99%. All volatiles were then distilled off at 120° C. and 3 mbar vacuum by slight degassing. Filtration gave a liquid silicone acrylate having a hydroxyl number of 27 mg KOH / g.

[0348] In a 0.5 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 200.6 g of the silicone acrylate thus prepared was mixed with 70.3 g of acetone, 33.8 g of EP-DC 1241 and 0.23 g of TIB KAT716LA were mixed and stirred for 4 hours at 60° C. A light green transparent product was obtained by distillation at 60° C. and 1-2 mbar with a small amount of gas release, and its viscosity at 25° C. was 857 mPa·s.

[0349] S8) preparing a silicone urethane acrylate according to formula (F) wherein m1=2, m2=0, m3=0, d1=65, d2=4, d3=t=q=0, x1=3, (x2=1 and x3=0) or (x2=1 and x3=0), R=CH3, R 1 =H, R 2 = Formula (H), R 3 = Formula (I), R 4 =H, and R 5 =Formula (J).

[0350] A 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer was charged with 37.29 g of acrylic acid, 0.073 g of methylhydroquinone, 21.13 g of n-butanol, 0.887 g of 2-(((3-(octyloxy)propyl)imino)methyl)phenol prepared according to EP 3168273A1 and 0.422 g of a 50% aqueous solution of chromium(III) acetate, while stirring. Heat to 115° C. while adding 666.64 g of a [polydimethyl(methyl-, glycidyloxypropyl)]-siloxane copolymer having a statistically distributed epoxy value of 1.08% by weight and a viscosity of 145 mPa·s at 25° C. Stirring was continued at 115° C.-120° C. until the conversion of epoxy groups, as determined by the acid number, was >99%. All volatiles were then distilled off at 120° C. and a vacuum of 3 mbar by slight degassing. Liquid silicone acrylate having a hydroxyl value of 33.8 mg KOH / g was obtained by filtration.

[0351] In a 1 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 215.8 g of the silicone acrylate thus prepared was mixed with 77.9 g of acetone, 43.9 g of EP-DC 1241 and 0.25 g of TIB KAT716LA were mixed and stirred at 60° C. for 4 hours. A brown transparent product was obtained by distillation at 60° C. and 3 mbar with a small amount of gas release, and its viscosity at 25° C. was 20004 mPa·s.

[0352] S9) preparing a silicone urethane acrylate according to formula (F) wherein m1=2, m2=0, m3=0, d1=89, d2=6, d3=0, t=q=0, x1=3, (x2=1 and x3=0) or (x2=1 and x3=0), R=CH3, R 1 =H, R 2 = Formula (H), R 3 = Formula (I), R 4 =H, and R 5 =Formula (J).

[0353] A 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer was charged with 167.5 g of acrylic acid, 0.27 g of methylhydroquinone, 79.7 g of n-butanol, 3.35 g of 2-(((3-(octyloxy)propyl)imino)methyl)phenol prepared according to EP 3168273 A1 and 1.60 g of a 50% aqueous solution of chromium(III) acetate, while stirring. Heating to 115° C., 2478.3 g of a statistically distributed [polydimethyl(methyl-, glycidyloxypropyl)]-siloxane copolymer with an epoxy group value of 1.39% by weight was added. Stirring was continued at 115° C.-120° C. until the conversion of epoxy groups, as determined by the acid number, was >97%. All volatiles were then distilled off at 120° C. and a vacuum of 1 mbar by slight degassing. The filtration gave a liquid silicone acrylate having a hydroxyl value of 47 mg KOH / g and a viscosity of 760 mPa*s at 25°C.

[0354] In a 1L four-necked flask equipped with a mechanical stirrer, a reflux condenser and an internal thermometer, 2124.8 g of the prepared silicone acrylate was mixed with 825 g of acetone, 625.1 g of EP-DC 1241, 0.28 g of methylhydroquinone and 5.5 g of TIB KAT 716LA were mixed and stirred for 6 hours at 60° C. A brown transparent product was obtained by distillation at 60° C. and 1 mbar with a small amount of gas release, and its viscosity at 25° C. was 528 Pa·s.

[0355] The silicone urethane (meth)acrylates are listed in Table 1. The silicone urethane (meth)acrylates according to the invention have a lower viscosity than silicone urethane (meth)acrylates not according to the invention.

[0356]

[0357] Table 1 (continued): Silicone urethane (meth)acrylates according to formula (F) - component (a)

[0358] Example Viscosity, 25℃(mPa·s) Number of acrylate groups Number of urethane groups <![CDATA[S1 [1] ]]> ～80.000 4 4 <![CDATA[S2 [1] ]]> 1.837 3 2 <![CDATA[S3 [1] ]]> 18.216 4 4 <![CDATA[S4 [2] ]]> solid 4 8 <![CDATA[S5 [2] ]]> solid 4 8 <![CDATA[S6 [2] ]]> solid 2 4 <![CDATA[S7 [2] ]]> 1350 2 2 <![CDATA[S8 [1] ]]> 20.004 8 8 <![CDATA[S9 [1] ]]> <![CDATA[528·10 3 ]]> 12 6

[0359] [1] According to the present invention

[0360] [2] Not according to the present invention

[0361] [3]x2+x3=1

[0362] Component (b) – Organic (meth)acrylate (reactive diluent)

[0363] The organic (meth)acrylates which have been used as component (b) are listed in Table 2.

[0364] Table 2: Organic (meth)acrylates - component (b)

[0365]

[0366] Component (c) – Silicone (meth)acrylate without urethane groups

[0367] Component (c1): Silicone (meth)acrylate according to formula (Q)

[0368] Silicone (meth)acrylates S10, S12 and S13 according to formula (Q) were prepared according to prior art methods, as described, for example, in EP 0940422 A1. The silicone (meth)acrylates according to formula (Q) are listed in Table 3.

[0369] Table 3: Silicone (meth)acrylates according to formula (Q) - component (c1)

[0370]

[0371] Component (c2): Silicone (meth)acrylate according to formula (S)

[0372] Silicone (meth)acrylates according to formula (S) are prepared according to the methods of the prior art, as disclosed in, for example, EP3168273A1 or WO 2017187030 A1. Silicone (meth)acrylates according to formula (S) are listed in Table 4.

[0373] Table 4: Silicone (meth)acrylates according to formula (S) - component (c2)

[0374] Example m1 d1 d2 d3 x1 R <![CDATA[R A ]]> <![CDATA[R 4 ]]> <![CDATA[R AC ]]> <![CDATA[R 5 ]]> S14 2 13 4 1 3 <![CDATA[CH3]]> Formula (K) and / or (L) H Formula (T) and / or (U) <![CDATA[CH3]]> S15 2 90 6 1 3 <![CDATA[CH3]]> Formula (K) and / or (L) H Formula (T) and / or (U) <![CDATA[CH3]]>

[0375] Barrier coating

[0376] Preparation of barrier coating:

[0377] The performance tests of the inventive synthesis example S1 were carried out in a formulation for release coatings. Release coatings are known in the prior art, especially in the form of release coatings on sheet-like supports and in particular for use in adhesive tapes or label laminates.

[0378] In each case, 78 g of silicone urethane acrylate from Synthesis Example S1, 20 g of hexanediol diacrylate and 2 g of photoinitiator were mixed vigorously. A18 (Evonik Industries AG, Germany) was used to prepare the formulation for the release coating.

[0379] The coating composition thus prepared was applied to a sheet-like support. This consisted of a 50 cm wide biaxially oriented polypropylene film (BoPP) which, before the coating composition was applied, had in each case been corona pretreated with a generator output of 1 kW. A 5-roll coating unit (Coating Machinery GmbH, Dormagen, Germany) was used at a rate of about 1 g / m 2 The coating composition was applied at a coating weight of 1000 W / cm and exposed to a stream of 100 m / min of water in a nitrogen atmosphere having a residual oxygen content of less than 50 ppm. Metz GmbH The film is cured by UV light from a medium-pressure mercury vapor lamp from Germany).

[0380] The samples thus coated were tested with respect to rub-off, release force, residual adhesion and abrasion resistance.

[0381] Separation force:

[0382] The release effect of adhesive materials, which are usually in the form of tapes or labels in industrial applications, is expressed by the release force (RF), with a low release force indicating a good release effect. The release force depends on the quality of the release coating, the adhesive itself and the test conditions. When evaluating the release coating, it is necessary to use the same adhesive and the same test conditions. To determine the release force, the tape or label laminate is cut into 2.5 cm widths and the adhesive side is then applied to the silicone coating being tested in each case. The test is carried out according to the test protocol FTM 10 in the FINAT manual 8th edition, The Hague / NL, 2009, with the modification that the storage is carried out at 40°C under pressure. The adhesive tape used is 7475 (trademark Tesa SE, Hamburg, Germany). The reported values ​​are the average of five replicate determinations in cN / 2.5 cm. The results are shown in Table 5.

[0383] Residual Adhesion:

[0384] The residual adhesion (RAF) was determined according to test protocol FTM 11 of the FINAT manual 8th edition, The Hague / NL, 2009, with the modification that the storage time of the test tape in contact with the silicone was one minute and the standard surface was an untreated BoPP surface. The tape used was 7475 (trademark Tesa SE, Hamburg, Germany). The residual adhesion is a measure of the crosslinking of the silicone. If unpolymerized and therefore migrating silicone components are present, the residual adhesion value decreases with increasing proportion of such components. The results are shown in Table 5.

[0385] Abrasion resistance:

[0386] The abrasion resistance was determined by means of an electronic Crockmeter M238BB with an adapted test setting for release coatings. The paper weight was 300 g / m 2 The coated BoPP substrate was impacted at a rate of 60 impacts / minute using a 6 cm x 6 cm black cardboard and 9 N power. The scratched film substrate was evaluated by classification on a scale of 1 to 10, where 1 has very poor abrasion resistance and 10 is very good and has no visible scratches or abrasions. The results are shown in Table 5.

[0387] Table 5: Performance test results (Resistance force (RF) after storage at 40°C for 24 hours, in cN / 25mm; % residual adhesion (RAF) and abrasion resistance; mass ratio of reactive diluent to silicone urethane acrylate is 1.5:1).

[0388]

[0389]

[0390] [1] According to the present invention

[0391] [2] Not according to the present invention

[0392] Table 5 shows formulations with a fixed silicone urethane acrylate to reactive diluent (HDDA) ratio while varying the content of pure silicone acrylate. It can be seen that within a specific window of silicone acrylate concentration (up to about 16%), the release force decreases while the abrasion resistance increases, which is surprising and highly advantageous. When the silicone acrylate content is increased further up to 33% of the formulation, the release force decreases further, but the abrasion resistance is now reduced, which is less desirable.

Claims

1. A composition comprising or consisting of the following components: (a) at least one silicone urethane (meth)acrylate having - at least three (meth)acrylate groups, and - no more urethane groups than (meth)acrylate groups, preferably as many urethane groups as (meth)acrylate groups; (b) at least one organic (meth)acrylate not having any silicon atoms; (c) at least one silicone (meth)acrylate not having any urethane groups; (d) optionally at least one curing catalyst; (e) optionally at least one additive; (f) optionally at least one solvent; Features: Based on the total weight of the sum of components (a) to (f) and / or based on the total weight of the composition, preferably based on the total weight of the composition, the composition contains - 20 to 70% by weight, preferably 25 to 50% by weight, more preferably 25 to 50% by weight of component (a); - 20 to 80% by weight, preferably 30 to 70% by weight, more preferably 40 to 65% by weight of component (b); - 1 to 60% by weight, preferably 2 to 40% by weight, more preferably 5 to 25% by weight of at least component (c); - 0 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.5 to 2.5% by weight of component (d); - 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 0 to 5% by weight of component (e); - 0 to 10% by weight, preferably 0 to 5% by weight, more preferably 0 to 1% by weight of component (f).

2. The composition according to claim 1, characterized in that The silicone urethane (meth)acrylate has m (meth)acrylate groups and n urethane groups, wherein m is an integer of at least 3, preferably 3 to 5, more preferably 4; n is an integer of at least 2, preferably 2 to 4, more preferably 4; The condition is m≥n, preferably m=n.

3. The composition according to claim 1 or 2, characterized in that The silicone urethane (meth)acrylate is represented by formula (B), X(-Y) p Formula (B), in X is a p-valent silicone group; Y is bonded to the silicon atom of the silicone group, and are independently selected in each case from monovalent organic groups having at least one urethane group and at least one (meth)acrylate group, is preferably independently selected in each case from monovalent organic groups having two (meth)acrylate groups and one or two urethane groups, More preferably, independently in each case are selected from monovalent organic groups having two (meth)acrylate groups and two urethane groups; p is an integer of at least 1, preferably 2 to 4, more preferably 2.

4. The composition according to any one of claims 1 to 3, characterized in that The silicone urethane (meth)acrylate comprises a unit represented by formula (C), [R a Y b SiO (4-a-b) / 2 Formula (C), in a is an integer from 0 to 2, preferably 1 or 2; b is an integer from 1 to 3, preferably 1; The condition is that a+b is 1 to 3; R is independently selected in each case from monovalent organic groups without any carbamate groups, is preferably independently selected in each case from monovalent hydrocarbon radicals having 1 to 30 carbon atoms, More preferably, it is methyl; Y is as defined in claim 3.

5. The composition according to any one of claims 1 to 4, characterized in that The silicone urethane (meth)acrylate comprises a group of formula (A), preferably contained in a group Y as defined in claim 3: Formula (A), in Z 1 is independently selected at each occurrence from -CH3 and -H, preferably -H; Z 2 is a divalent organic group, preferably an alkylene group, preferably derived from OCN-Z 2 -Alkylene of isophorone diisocyanate of diisocyanate of CNO; Z 3 is a (q+1)-valent organic group, wherein q is an integer of 1 to 3, preferably an alkylene group, preferably -(C2H4)-; Z 4 is independently selected at each occurrence from -CH3 and -H, preferably -H; And wherein each dashed line represents a covalent bond.

6. The composition according to any one of claims 1 to 5, characterized in that The silicone urethane (meth)acrylate is represented by formula (F), M m1 M UA m2 M A m3 D d1 D UA d2 D A d3 T t Q q Formula (F), in 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 from 0 to 32, preferably from 0 to 22, more preferably 0; m2 is an integer from 0 to 32, preferably from 1 to 10, more preferably 2; m3 is an integer from 0 to 32, preferably from 0 to 22, more preferably 0; d1 is an integer from 1 to 1000, preferably from 5 to 500, more preferably from 10 to 400; d2 is an integer from 0 to 10, preferably from 0 to 5, more preferably 0; d3 is an integer from 0 to 10, preferably from 0 to 5, more preferably 0; t is an integer from 0 to 10, preferably from 0 to 5, more preferably from 1 to 5; q is an integer from 0 to 10, preferably from 0 to 5, more preferably from 1 to 5; The conditions are: m1+m2+m3 is at least 2, preferably 2 to 20, more preferably 2 to 10; m2+d2 is at least 1, preferably 2 to 10, more preferably 2 to 6; in R is independently selected in each case from monovalent organic groups without any urethane groups or (meth)acrylate groups, is preferably independently selected in each case from monovalent hydrocarbon radicals having 1 to 30 carbon atoms, More preferably, it is methyl; R UA are independently selected in each case from monovalent organic groups having at least one (meth)acrylate group and at least one urethane group, is preferably independently selected in each case from monovalent organic groups having two (meth)acrylate groups and one or two urethane groups, More preferably, each occurrence is independently selected from the monovalent organic groups represented by formula (G), Formula (G); x1 is an integer from 1 to 3, preferably 3; R 1 is independently selected at each occurrence from a hydrogen radical, a monovalent hydrocarbon radical having 1 to 6 carbon atoms, 2 and R 3 ; is preferably independently selected at each occurrence from a hydrogen radical and a monovalent hydrocarbon radical having 1 to 6 carbon atoms, More preferably, it is a hydrogen group; R 2 is independently selected at each occurrence from a hydrogen group, an R 3 and a monovalent organic group having at least one (meth)acrylate group; Preferably, each occurrence is independently selected from R 3 and a monovalent organic group having at least one (meth)acrylate group; More preferably, each occurrence is independently selected from monovalent groups of formula (H) x2=(1-x3); R 3 are independently selected in each case from monovalent organic groups having at least one urethane group and at least one (meth)acrylate group; are preferably independently selected in each case from monovalent organic groups having exactly two urethane groups and exactly one (meth)acrylate group; More preferably, each occurrence is independently selected from monovalent organic groups of formula (I), x3 is an integer from 0 to 1, preferably 0; R 4 is independently selected at each occurrence from a hydrogen group or a methyl group, preferably a hydrogen group; R 5 is independently selected in each case from a divalent, saturated or unsaturated, linear or branched or cyclic hydrocarbon radical having 1 to 30 carbon atoms; Preferably it is a divalent group of formula (J), R A are independently in each case selected from monovalent organic groups having at least one (meth)acrylate group but no urethane group; Preferably, each occurrence is independently selected from monovalent groups represented by formula (K) or (L); More preferably, each occurrence is independently selected from the monovalent groups represented by formula (K); where x1 and R 4 As defined above.

7. The composition according to any one of claims 3 to 6, characterized in that R UA or Y is represented by at least one of formula (M), (N), (O) and (P):

8. The composition according to any one of claims 1 to 7, characterized in that The at least one silicone (meth)acrylate of component (c) is represented by formula (Q) and / or the at least one silicone (meth)acrylate of component (c) is represented by formula (S), M A m1 D d1 Formula (Q); in M A =[R2(R A )SiO 1 / 2 ]; D=[R2SiO 2 / 2 ]: m1 is an integer of 2; d1 is an integer from 1 to 10000, preferably from 50 to 5000, more preferably from 70 to 2000; in R is independently selected in each case from monovalent organic groups without any urethane groups or (meth)acrylate groups, is preferably independently selected in each case from monovalent hydrocarbon radicals having 1 to 30 carbon atoms, More preferably, it is methyl; R A are independently in each case selected from monovalent organic groups having at least one (meth)acrylate group but not one urethane group; Preferably, each occurrence is independently selected from monovalent groups represented by the formula (R), x1 as defined in claim 6; x4 is an integer 0 or 1, preferably 0; R 6 is independently selected at each occurrence from monovalent hydrocarbon groups having 1 to 6 carbon atoms; Preferably ethyl; R 7 are independently in each case selected from monovalent organic groups having at least one (meth)acrylate group but no urethane group; is preferably independently selected in each case from monovalent groups of formula (H) as defined in claim 6; M m1 D d1 D A d2 D AC d3 Formula (S); in M=[R3SiO 1 / 2 ]; D=[R2SiO 2 / 2 ]: D A =[R(R A )SiO 2 / 2 ]; D AC =[R(R AC )SiO 2 / 2 ]; in: R, m1 and d1 are as defined for formula (Q); d2 is an integer from 1 to 20, preferably from 2 to 10, more preferably from 3 to 8; d3 is an integer from 0 to 3, preferably from 0 to 2, more preferably from 0 to 1; R A are independently in each case selected from monovalent organic groups having at least one (meth)acrylate group but no urethane group; Preferably, each occurrence is independently selected from monovalent groups represented by formula (K) or (L); More preferably, each occurrence is independently selected from the monovalent groups represented by formula (K); where x1 and R 4 As defined in claim 6; R AC independently in each case selected from monovalent organic groups having at least one carboxylate group but no (meth)acrylate groups and urethane groups; Preferably, independently in each case, selected from monovalent groups represented by formula (T) or (U), wherein x1 is as defined in claim 6; R 5 is independently selected at each occurrence from monovalent hydrocarbon groups having 1 to 22 carbon atoms; Preferred is methyl.

9. The composition according to any one of claims 1 to 8, characterized in that The composition is curable, preferably by a free radical reaction, which can be initiated thermally, by UV radiation and / or by electron beams.

10. A method for preparing a composition according to any one of claims 1 to 9, comprising or consisting of the following steps: (i) preparing a mixture of component (a) and component (f); (ii) preparing a mixture by adding at least one of the components (b) to (e), preferably components (b) and / or (c), to the mixture of step (i); (iii) removing the component (f) from the mixture of step (ii); (iv) Optionally, if at least one of the components (b) to (e) is not added in step (ii), preparing a mixture by adding at least one of the components (b) to (e) to the mixture of step (iii).

11. A method for preparing a barrier coating, a protective film or a protective coating, comprising the following steps, either directly or indirectly, in succession: a. applying the composition according to any one of claims 1 to 9 to a surface; b. Curing the composition, preferably by irradiation with UV radiation.

12. A barrier coating, a protective film or a protective coating obtainable by curing a composition according to any one of claims 1 to 10, preferably obtainable by a process according to claim 11.

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