Methods for preparing membranes and compositions thereof

Abstract

This invention discloses a method for preparing a film, the method comprising applying a composition onto a substrate to obtain an uncured layer. The method further comprises irradiating the uncured layer to obtain the film. The composition comprises: (a) a polysiloxane resin, (b) a photoinitiator, and optionally (c) a functional diluent. The (a) polysiloxane resin includes acryloyloxy functionality and an average concentration of OZ groups of at least 12 mol% relative to the molar number of silicon atoms in the (a) polysiloxane resin, wherein Z is independently an H or alkyl group.

Description

[0001] Cross-references to related applications

[0002] This patent application claims priority and all advantages of U.S. Provisional Patent Application No. 63 / 126,727, filed on December 17, 2020, the contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to a method for preparing a membrane, and more specifically, to a method for preparing a membrane by irradiation and a composition for use therein. Background Technology

[0004] Organosilicon resins are known in the art and used in a variety of end-use applications. Organosilicon resins typically comprise components attributable to the presence of T-silyloxy units (R...). 0 SiO 3 / 2 ) and / or Q-methylsilyloxy units (SiO) 4 / 2 A three-dimensional network, where R 0 Substituents. The properties of silicone resins vary depending on their crosslinking density and the molar fraction of silanoxy units, etc. Increasing the crosslinking density generally results in greater hardness and / or stiffness.

[0005] For the purpose of formulating a curable composition, a silicone resin is typically functionalized. The curable composition containing the functionalized silicone resin can then be cured, for example, by reacting with a reactive component (e.g., a crosslinking agent) and / or by exposure to curing conditions. For example, a curable composition containing a functionalized silicone resin can be cured by heat, moisture, irradiation, etc., depending on the functionalized silicone resin used.

[0006] Conventional silicone resins are solids at room temperature or 25°C. Therefore, conventional curable compositions containing conventional silicone resins are typically solvent-based, as a solvent is required to dissolve the silicone resin. The solvent is usually removed or evaporated before or during the end-use application of the conventional curable composition. However, removing the solvent increases the processing steps and costs associated with the end-use application of conventional curable compositions utilizing such solid silicone resins. Furthermore, solvent removal typically requires elevated temperatures, which is unsuitable for certain end-use applications of silicone resins (e.g., when installed on certain electronic devices).

[0007] UV curing of silicone compositions is commonly used to prepare films and coatings that require curing without heat. However, if the silicone composition contains conventional silicone resins, it is typically solvent-based, which, as mentioned above, still requires elevated temperatures, even if not for curing. If the silicone composition is solvent-free, it is typically based on linear and / or partially branched organopolysiloxanes with low viscosity and liquid properties at room temperature. However, the use of linear organopolysiloxanes results in a lower crosslinking density in the film or coating compared to films formed via silicone resins, which reduces the film's or coating's hardness and other properties, potentially leading to undesirable consequences.

[0008] Furthermore, some substrates on which films or coatings are formed may have complex geometries or surface properties, creating shaded areas that are difficult to cure via UV radiation. Therefore, a dual-curing system is often required, capable of curing via both UV radiation and moisture (or another curing mechanism that does not require elevated temperatures). However, conventional silicone resins do not contain sufficient functional groups to achieve both UV and moisture curing simultaneously, necessitating the use of linear organopolysiloxanes. Summary of the Invention

[0009] This invention discloses a method for preparing a film, which may alternatively be referred to as a coating. The method includes applying a composition onto a substrate to obtain an uncured layer. The method further includes irradiating the uncured layer to obtain the film. The composition comprises: (a) a polysiloxane resin, (b) a photoinitiator, and optionally (c) a functional diluent. (a) The polysiloxane resin comprises the following silanoxy units: [R3SiO 1 / 2 ]、[(OZ) q SiO (4-q) / 2 And at least one of the following: [(OZ)] t R MA SiO (3-t) / 2 [] or [(OZ)] d RR MA SiO (2-d) / 2 ]; where: each R is independently a substituted or unsubstituted hydrocarbon group, each R MA Each Z is independently an acryloyloxy functional group, each Z is independently an H or alkyl group, the subscript q is a number selected from the range of 0-3 each time it appears, the subscript t is a number selected from the range of 0-2 each time it appears, and the subscript d is a number selected from the range of 0-1 each time it appears, provided that the average concentration of the OZ group is at least 12 mol relative to the number of moles of silicon atoms in (a) the polysiloxane resin.

[0010] The composition for preparing the membrane and the membrane formed by the method are also disclosed. Detailed Implementation

[0011] A method for preparing a film using a composition, and the composition for preparing the film, are disclosed and described below. The composition can be cured by exposure to UV radiation and can also be dual-cured by a combination of moisture (i.e., condensation) and irradiation. In some embodiments, it is desirable to form the film via dual curing of the composition to increase the crosslink density within the film and / or to cure in areas difficult to reach by irradiation (e.g., shaded areas). In other embodiments, as described below, the film can be formed solely by irradiation (moisture-free curing). For example, while not limited to this particular end-use application, films formed by this method possess excellent physical properties for use as protective and / or conformal coatings. Depending on the shape of the substrate on which the film is formed, dual-cured films ensure complete curing even in areas difficult for irradiation to penetrate or reach (e.g., due to the size and / or surface characteristics of the substrate).

[0012] The composition comprises: (a) a polysiloxane resin, (b) a photoinitiator, and optionally (c) a functional diluent.

[0013] (a) The polysiloxane resin contains the following silanoxy units: [R3SiO 1 / 2 ]、[(OZ) q SiO (4-q) / 2 And at least one of the following: [(OZ)] t R MA SiO (3-t) / 2 [] or [(OZ)] d RR MA SiO (2-d) / 2 In one embodiment, (a) the polysiloxane resin comprises [(OZ)] t R MA SiO (3-t) / 2 ] and [(OZ) d RR MA SiO (2-d) / 2 [Silyloxy unit]. In other embodiments, (a) the polysiloxane does not contain one of these types of silyloxy units, but contains other types of silyloxy units. In (a) the polysiloxane resin, each R is independently a substituted or unsubstituted hydrocarbon group, each R MA Each Z is independently an acryloyloxy functional group, each Z is independently an H or alkyl group, the subscript q is a number selected from the range of 0-3 each time it appears, the subscript t is a number selected from the range of 0-2 each time it appears, and the subscript d is a number selected from the range of 0-1 each time it appears, provided that the average concentration of the OZ group is at least 12 mol relative to the number of moles of silicon atoms in (a) the polysiloxane resin.

[0014] As described above, each R is an independently chosen hydrocarbon group. Generally, the hydrocarbon group suitable for R can be independently straight-chain, branched, cyclic, or a combination thereof. Cyclic hydrocarbon groups include aryl groups as well as saturated or non-conjugated cyclic groups. Cyclic hydrocarbon groups can be independently monocyclic or polycyclic. Straight-chain and branched hydrocarbon groups can be independently saturated or unsaturated. An example of a combination of straight-chain and cyclic hydrocarbon groups is an aralkyl group. General examples of hydrocarbon groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., and their derivatives, modifications, and combinations. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, octadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl groups. Examples of suitable monovalent haloalkyl groups (i.e., hydrocarbon groups) include haloalkyl groups, aryl groups, and combinations thereof. Examples of haloalkyl groups include alkyl groups in which one or more hydrogen atoms of the above are replaced by halogen atoms such as F or Cl. Specific examples of halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, and their derivatives. Examples of halogenated aryl groups include aryl groups in which one or more of the hydrogen atoms of the above groups are replaced by halogen atoms such as F or Cl. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups.

[0015] In some embodiments, each R is free of aliphatic unsaturation (i.e., each R is not an alkenyl or alkynyl group). In these or other embodiments, each R is independently an alkyl or aryl group. In a specific embodiment, each R is independently selected from alkyl groups having 1 to 32, alternatively 1 to 28, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 8, alternatively 1 to 4, or alternatively 1 carbon atom.

[0016] Each R MA Independently, it is an acryloyloxy functional group. Typically, each R... MA Independently possessing the following formula:

[0017]

[0018] Where X is a covalent bond or a divalent linker, and R 1 It is an H or alkyl group. Applicable to R 1 The alkyl group is disclosed above for R. In some embodiments, R 1 Let H be such that R MA It can be defined as an acrylate group. In other embodiments, R 1 The presence of an alkyl group makes R MA It can be defined as an alkyl acrylate group. In a specific embodiment, R 1 The methyl group makes R MA X can be defined as a methacrylate group. In one embodiment, X is a covalent bond. In other embodiments, X is a divalent linker. The divalent linker is not limited and can be organic or, for example, a silyloxy moiety. Typically, when X is a divalent linker, X is a divalent hydrocarbon group. Suitable hydrocarbon groups of the divalent linker can be substituted or unsubstituted and are straight-chain, branched, and / or cyclic. However, typically, when the divalent linker is a divalent hydrocarbon group, X is a straight-chain unsubstituted hydrocarbon group comprising 1 to 12, alternatively 1 to 10, alternatively 1 to 8, alternatively 1 to 6, or alternatively 1 to 4 carbon atoms.

[0019] Each Z is independently an H or alkyl group, and therefore each OZ moiety is independently a hydroxy or alkoxy group each time it appears. In specific embodiments, each OZ is independently selected from hydroxy, methoxy, and ethoxy groups each time it appears. Increasing the OZ content generally increases the flowability of the (a) polysiloxane resin (reduces its viscosity) and increases the rate at which the composition can be moisture-cured to form a surface layer during moisture curing (reduces the required time). Increasing the OZ content also tends to increase glass adhesion. Therefore, a higher OZ content may be desired to enhance those properties. In some applications, the thermal stability of the (a) polysiloxane resin may be important, where the upper limit of the OZ content becomes crucial because the thermal stability of (a) polysiloxane resin tends to decrease with increasing OZ content. It may be desirable for the (a) polysiloxane resin to have a 5% weight loss temperature above 150°C (according to thermogravimetric analysis (TGA)). To achieve this type of thermal stability, an OZ content of, for example, 80 mol% or less, alternatively 60 mol% or less, alternatively 50 mol% or less, alternatively 40 mol% or less, alternatively 30 mol% or less, alternatively 20 mol% or less may be desired. In these or other embodiments, based on the total number of moles of Si per molecule, (a) the polysiloxane resin has a SiOZ fractional content of 12% to 80%, alternatively 15% to 70%, alternatively 15% to 60%, alternatively 15% to 50%, alternatively 15% to 40%, alternatively 15% to 30%. In this document, OZ content is relative to the number of moles of silicon atoms in the polysiloxane resin. Conventional silicone resins have much lower OZ contents, especially those containing functional groups such as acryloyloxy functional groups. For example, such functional groups are typically imparted to conventional silicones (e.g., via functionalized silanes) during the formation of conventional silicone resins. The formation of such conventional silicone resins typically involves the condensation of OZ groups to create siloxane bonds in the resulting silicone resin, thereby reducing the OZ content of the silicone resin.

[0020] The SiOZ content can be used 29 Si nuclear magnetic resonance spectroscopy ( 29 Si NMR) determination or measurement. 29 Si NMR can be performed, for example, using a Varian XL-400 spectrometer. Chemical shifts are referenced to internal solvent resonances and recorded relative to tetramethylsilane. Each siloxane unit in the resin appears at a unique position. Integrating the peak area allows calculation of the concentration of OZ groups relative to silicon atoms. Peaks in the spectrum are labeled with their corresponding siloxane units, as follows:

[0021] M = R3SiO 1 / 2

[0022] D1=R2(OZ)SiO 1 / 2

[0023] D2=R2SiO 2 / 2

[0024] T1=R(OZ)2SiO 1 / 2

[0025] T2=R(OZ)SiO 2 / 2

[0026] T3 = RSiO 3 / 2

[0027] Q1=(OZ)3SiO 1 / 2

[0028] Q2=(OZ)2SiO 2 / 2

[0029] Q3=(OZ)SiO 3 / 2

[0030] Q4 = SiO 4 / 2

[0031] The OZ content relative to silicon atoms in mol% can be calculated using the following formula, where the label of each peak corresponds to the area of ​​integration under that labeled peak:

[0032]

[0033] In some embodiments, (a) the polysiloxane is composed of [R3SiO] 1 / 2 ]、[(OZ) q SiO (4-q) / 2 ] and [(OZ) t R MA SiO (3-t) / 2 [] or [(OZ)] d RR MA SiO (2-d) / 2 At least one of the silanoloxy units. In other embodiments, (a) the polysiloxane may further comprise R2SiO 2 / 2 Unit (D-type unit) and / or RSiO 3 / 2Units (T-type units). D-type units may ideally be included to impart linear properties to the (a) polysiloxane resin, which typically decreases the film stiffness with increasing D-type unit concentration. In other embodiments, it may be desirable to increase the film stiffness. In such embodiments, it may be desirable to maintain the average concentration of D-type units in the (a) polysiloxane resin at 10 mol% or less, preferably 5 mol% or less, even more preferably 2 mol% or less, 1 mol% or less, or even 0.5 mol% or less, relative to the total moles of siloxane units. The (a) polysiloxane resin may be free of D-type siloxane units to achieve maximum stiffness in the film formed from the composition.

[0034] In a specific implementation, (a) the polysiloxane resin has the following average formula:

[0035] [W] a [X] b [Y] c [Z] d ,

[0036] Where subscript a is greater than 0 to 0.5; subscript b is 0 to 0.5; subscript c is greater than 0 to 0.5; and subscript d is greater than 0 to 0.6; the prerequisite is a+b+c+d=1. Subscripts a, b, c and d are the mole fractions of W, X, Y and Z units in (a) polysiloxane resin.

[0037] In the average formula of the polysiloxane resin in (a) above, [W], [X], [Y], and [Z] are used instead of the more common nomenclature [M], [D], [T], and [Q]. As understood in the art, the M-siloxane unit comprises one siloxane bond (i.e., -O-Si-); the D-siloxane unit comprises two siloxane bonds; the T-siloxane unit comprises three siloxane bonds; and the Q-siloxane unit comprises four siloxane bonds.

[0038] However, for the purposes of this disclosure, [W] indicates a silanoxy unit comprising a -Si-O- bond, which may be a siloxane bond or a precursor thereof, but is typically a siloxane bond. The precursor to a siloxane bond is a -Si-OZ bond, where Z is independently chosen and as defined above. Silanol and alkoxy groups can be hydrolyzed and / or condensed to yield a siloxane bond, and are typically inherently present in most silicone resins. Such precursors of siloxane bonds can be minimized by bodying the silicone resin, which allows for further condensation with water as a byproduct. Therefore, for the purposes of this disclosure, [W] indicates [R3SiO] 1 / 2 ], where each R is chosen independently and as defined above.

[0039] Furthermore, for the purposes of this disclosure, [X] indicates a silanoxy unit comprising two -Si-O- bonds, which may independently be a siloxane bond or a precursor thereof. Therefore, for the purposes of this disclosure, [X] is [R2SiO] 1 / 2 (OZ)] b’ [R2SiO 2 / 2 ] b” [RR MA SiO 2 / 2 ] b”’ [R MA SiO 1 / 2 (OZ)] b”” , where each R and R MA The following are independently selected and defined as above: 0 ≤ b' ≤ b; 0 ≤ b” ≤ b; 0 ≤ b”’ ≤ b; 0 ≤ b”” ≤ b; the premise is that b' + b” + b”’ + b”” corresponds to b in the above average formula; and each Z is independently selected and defined as above. Regarding the overall average formula of (a) polysiloxane resins, the subscripts b', b”, b”’, and b”” indicate the relative molar fraction of the [X]siloxane units indicated by each subscript. In the [X]siloxane units indicated by b' and b””, there is one siloxane bond and one Si-OZ bond, and in the [X]siloxane units indicated by b” and b”’, there are two siloxane bonds.

[0040] Furthermore, for the purposes of this disclosure, [Y] indicates a silanoxy unit comprising three -Si-O- bonds, which may independently be a siloxane bond or a precursor thereof. Therefore, for the purposes of this disclosure, [Y] is [R] MA Si(OZ) c' O 3-c' / 2 [ ] and / or [RSi(OZ ) c' O 3-c' / 2 ], where each R MA Each R is chosen independently and as defined above; c' is an integer from 0 to 2 and is chosen independently in each Y siloxy unit indicated by the subscript c in (a) the polysiloxane resin. Therefore, [Y] can indicate any combination of the following siloxy units: [R] MA SiO 3 / 2 ]、[R MA Si(OZ)1O 2 / 2 ]、[R MA Si(OZ)2O 1 / 2 ]、[RSiO 3 / 2 [RSi(OZ)1O] 2 / 2 ] and / or [RSi(OZ)2O 1 / 2 In some embodiments, (a) the polysiloxane does not contain [RSiO]. 3 / 2[RSi(OZ)1O] 2 / 2 [RSi(OZ)2O] and [RSi(OZ)2O] 1 / 2 [Silyloxy unit. If the silyloxy unit indicated by Y is R instead of R] MA Then R MA The group is usually present in the X-methoxy unit mentioned above.

[0041] Furthermore, for the purposes of this disclosure, [Z] indicates a silanoxy unit comprising four -Si-O- bonds, which may independently be a siloxane bond or a precursor thereof. Therefore, for the purposes of this disclosure, [Z] is [Si(OZ)]. d' O 4-d' / 2 [Z], where each Z is independently selected and as defined above, and the subscript d' is an integer from 0 to 3 and is independently selected in (a) the polysiloxane resin by the subscript c in each siloxane unit. (a) The polysiloxane resin may include siloxane units indicated by the subscript d, where d' is 0, d' is 1, d' is 2, and d' is 3. The siloxane unit represented by [Z] may have one, two, three, or four siloxane bonds, where the remainder is a Si-OZ portion. Therefore, [Z] may indicate any combination of the following siloxane units: [SiO 4 / 2 ]、[Si(OZ)O 3 / 2 [Si(OZ)2O] 2 / 2 ] and / or [Si(OZ)3O 1 / 2 ].

[0042] In some implementations, the subscript 'a' is greater than zero and ranges from 0.5. In specific implementations, the subscript 'a' is 0.10 to 0.50, alternatively 0.15 to 0.40, alternatively 0.2 to 0.4, alternatively 0.2 to 0.35, alternatively 0.25 to 0.30, alternatively 0.25 to 0.35, or alternatively 0.28 to 0.33.

[0043] In these or other embodiments, the subscript b is greater than zero and ranges from 0.5. In specific embodiments, the subscript b is 0.01 to 0.40, alternatively 0.02 to 0.30, alternatively 0.03 to 0.20, alternatively 0.04 to 0.15, alternatively 0.05 to 0.1. In other embodiments, the subscript b is 0. The subscripts b', b”, b”', and b”” define the relative amount of a specific siloxy group represented by [X].

[0044] In these or other implementations, the subscript c is greater than 0, for example, greater than zero to 0.5, alternatively 0.05 to 0.4, alternatively 0.1 to 0.3.

[0045] In these or other implementations, the subscript d is greater than zero and up to 0.6. In specific implementations, the subscript d is 0.35 to 0.60, alternatively 0.40 to 0.60, alternatively 0.40 to 0.55, alternatively 0.45 to 0.55, or alternatively 0.45 to 0.53.

[0046] In various embodiments, (a) the polysiloxane resin has a weight-average molecular weight of 1,000 to 100,000, alternatively 1,000 to 50,000, alternatively 1,000 to 10,000. The molecular weight can be measured relative to a polystyrene standard via gel permeation chromatography (GPC). In these or other embodiments, (a) the polysiloxane resin has a viscosity at 25°C of 10 cP to 500,000 cP, alternatively 10 cP to 250,000 cP, alternatively 10 cP to 100,000 cP. The viscosity can be measured at 25°C using a Brookfield LV DV-E viscometer with a rotor selected as suitable for the viscosity of (a) the polysiloxane resin as understood in the art. The viscosity and molecular weight of (a) the polysiloxane resin can be controlled during its preparation. In other embodiments, (a) the polysiloxane resin is a gel at 25°C, in which case (a) the polysiloxane resin may not have a viscosity that can be easily measured at 25°C, but still has the characteristic of being able to flow and is considered a liquid for the purposes of this disclosure.

[0047] In some embodiments, the (a) polysiloxane resin is liquid at 25°C in the absence of any solvent. Generally, silicone resins, and especially silicate resins, are solid at 25°C due to their three-dimensional network structure. Given the difficulty in processing solid silicone resins, they are typically dissolved in solvents and used as silicone resin compositions comprising or composed of solid silicone resins dissolved in solvents (e.g., aliphatic or aromatic hydrocarbon solvents). In this way, the silicone resin composition is liquid at 25°C or room temperature, which allows for easier processing. For example, the silicone resin composition can be combined with other components or compositions for use in liquid form in various end-use applications. Similarly, conventional silicone resins that are solid at 25°C in the absence of any solvent are not readily miscible with liquid silicones. This means that when preparing silicone compositions, conventional silicone resins that are solid at 25°C cannot be readily mixed or dissolved with liquid silicones, such as liquid organopolysiloxanes, in the absence of organic solvents. Therefore, when conventional silicone resins are used in silicone compositions, organic solvents are typically required for the purpose of forming the silicone composition and subsequently evaporate in the form of the composition or during curing.

[0048] However, one drawback of silicone compositions is that the solvent is typically removed during the end-use application. For example, when silicone compositions are used to form films, coatings, or articles, the solvent is usually removed during the formation of such films or articles. This requires additional processing steps and incurs energy and associated costs, such as solvent removal through evaporation.

[0049] In contrast, the (a) polysiloxane resin of this invention is typically liquid at 25°C in the absence of any solvent. Therefore, unlike conventional silicone resins, this (a) polysiloxane resin is liquid at 25°C not due to the presence of any solvent, such as an organic solvent. This (a) polysiloxane resin consists of (a) polysiloxane resins free of any solvent or carrier medium. Furthermore, in terms of preparation and final composition, the (a) polysiloxane resin is not only liquid at 25°C in the absence of any solvent, but it is also miscible with other liquid organopolysiloxanes, allowing the (a) polysiloxane resin to be directly incorporated into various silicone compositions in a solvent-free form.

[0050] "Liquid" means that (a) polysiloxane resin is flowable at 25°C and / or has a measurable viscosity at 25°C in the absence of any solvent. Typically, the viscosity of (a) polysiloxane resin can be measured at 25°C using a Brookfield LV DV-E viscometer with a rotor selected to suit the viscosity of (a) polysiloxane resin. The viscosity of (a) polysiloxane resin can vary, particularly based on the content of M, D, T, and / or Q siloxy units present therein, as described below. However, for the purposes of this disclosure, (a) polysiloxane resin can be in the form of a gel, as gels still possess the characteristic of being flowable, even if the gel does not have a viscosity that can be easily measured at 25°C.

[0051] In various embodiments, (a) the polysiloxane resin is prepared from MQ resin, where M represents (R 0 SiO 3 / 2 ) silyloxy group, and Q represents (SiO) 4 / 2 ) silyloxy unit, wherein R 0 Substituents representing silicon bonds. Such MQ resins are known in the art and are typically in solid form (e.g., powder or flakes) unless disposed in a solvent. However, in the nomenclature commonly used in the art, the M-methylsiloxy unit is a trimethylsiloxy unit, and MQ resins may include hydrocarbon groups other than methyl groups. However, typically, the M-methylsiloxy unit of MQ resins is a trimethylsiloxy unit.

[0052] MQ resin can have formula M zQ, where the subscript z refers to the molar ratio of M siloxy units to Q siloxy units when the molar number of Q siloxy units is normalized to 1. A larger value of z indicates a lower crosslinking density in the MQ resin. Conversely, a smaller value of z indicates a lower number of M siloxy units, and therefore more Q siloxy units network without being capped by M siloxy units. The fact that the formula of the MQ resin normalizes the content of Q siloxy units to 1 does not mean that the MQ resin comprises only one Q unit. Typically, the MQ resin comprises multiple Q siloxy units aggregated or bonded together. In some embodiments, the MQ resin may comprise up to 4 wt%, alternatively up to 3 wt%, alternatively up to 2 wt% of hydroxyl groups. In these or other embodiments, based on the total number of siloxy units, the MQ resin contains >1 to <12, alternatively 8 > to <11.5 mol% of SiOH groups. (a) The polysiloxane resin contains a higher molar percentage of SiOZ groups than the SiOH groups in the MQ resin.

[0053] In specific embodiments, the subscript z < 1, for example, z is 0.05 to 0.99, alternatively 0.10 to 0.95, alternatively 0.15 to 0.90, alternatively 0.25 to 0.85, alternatively 0.40 to 0.80. In these embodiments, based on molarity, there are more Q silanoxy units in the MQ resin than M silanoxy units. However, in other embodiments, z may be > 1, for example > 1 to 6, alternatively > 1 to 5, alternatively > 1 to 4, alternatively > 1 to 3, alternatively > 1 to 2.

[0054] In a specific embodiment, to prepare (a) a polysiloxane resin from MQ resin, the MQ resin is reacted with a silane component containing a silane compound in the presence of a catalyst. The silane compound typically has the formula R MA R x Si(OR 2 ) 3-x , where R MA As defined above, each R... 2 It is an independently chosen alkyl group, and the subscript x is 0 or 1. Silane compounds include silicon-bonded acryloyloxy groups (determined by R...). MA (Indication) and two or three silicon-bonded alkoxy groups. When the subscript x is zero, the silane compound includes three silicon-bonded alkoxy groups. When x is one, the silane compound includes two silicon-bonded alkoxy groups. Silane compounds are used via R MAAcryloyloxy functionality is imparted to (a) the polysiloxane resin. The silicon-bonded alkoxy group can be independently selected and typically has 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 or 2, or alternatively 1 carbon atom. For example, the silicon-bonded alkoxy group can be methoxy, ethoxy, propoxy, butoxy, etc. When the subscript x is 1, the silane compound is represented by [RR...] MA SiO 2 / 2 The silanoxy group, represented by [R], is introduced into (a) polysiloxane resin. When the subscript x is 0, the silane compound is represented by [R]. MA SiO 3 / 2 The siloxane group represented by ] is introduced into (a) polysiloxane resin.

[0055] Combinations of different silane compounds can be used in silane components. For example, different types of silane compounds can be used together in a silane component. Furthermore, in some embodiments, the silane component also comprises compounds having the formula R2Si(OR) 2 The second silane compound, wherein R and R 2 Each is selected independently and as defined above. In these embodiments, the second silane compound is formed by [R2SiO2]. 1 / 2 (OZ)] and / or [R2SiO] 2 / 2 The silane group represented by ] is introduced into (a) the polysiloxane resin. In these or other embodiments, the silane component may also contain a group having the formula RSi(OR) 2 The third silane compound, wherein R and R 2 Each is selected independently and as defined above. In these embodiments, the third silane compound is used as a [RSiO] 1 / 2 (OZ)2]、[RSiO 2 / 2 (OZ)] and / or [RSiO 3 / 2 The siloxane group represented by ] is introduced into (a) polysiloxane resin.

[0056] In the method for preparing (a) polysiloxane resin, a catalyst typically cleaves the siloxane bonds of the MQ resin, usually between the M and Q siloxane units, to yield SiOZ groups, where Z is defined above. The silane compound of the silane component can be hydrolyzed and condensed with the SiOZ group to be incorporated therein. The cleaved siloxane bonds and the inclusion of linear siloxane units attributable to the silane compound both result in (a) polysiloxane resin being liquid at 25°C in the absence of any solvent.

[0057] The relative amount of silane component used compared to MQ resin is a function of the desired subscripts b and c in (a) the polysiloxane resin. In view of the description herein, including the examples following this detailed description, those skilled in the art will understand how such content can be selectively controlled.

[0058] MQ resin and silane compounds react in the presence of a catalyst. Typically, the catalyst is an acid or a base, making the reaction between the MQ resin and the silane component either acid-catalyzed or base-catalyzed. Typically, the reaction is base-catalyzed. Therefore, in some embodiments, the catalyst may be selected from the group consisting of strong acid catalysts, strong base catalysts, and combinations thereof. Strong acid catalysts may be trifluoromethanesulfonic acid, etc. Catalysts are typically strong base catalysts. Typically, strong base catalysts are KOH, but other base catalysts, such as phosphazene base catalysts, can be used.

[0059] Phosphazene catalysts typically contain at least one —(N=P<)- unit (i.e., a phosphazene unit) and are generally oligomers having up to 10 such phosphazene units (e.g., having an average of 1.5 to a maximum of 5 phosphazene units). Phosphazene catalysts can be, for example, halophosphazenes, such as chlorophosphazenes (phosphazene chlorides), oxyhalophosphazenes, ionic derivatives of phosphazenes, such as phosphazene salts, particularly ionic derivatives of phosphazene halides, such as perchlorinated oligomeric phosphazene salts or their partially hydrolyzed forms.

[0060] In a specific embodiment, the catalyst comprises a phosphazene base catalyst. The phosphazene base catalyst can be any known in the art, but typically has the following chemical formula:

[0061] ((R 4 2N)3P=N) p (R 4 2N) 3-p P=NR 4

[0062] Each R 4 Independently selected from the group consisting of hydrogen atoms, R, and combinations thereof, where p is an integer from 1 to 3. If R 4 If it is R, then R 4 Typically, it has alkyl groups having 1 to 20, alternatively 1 to 10, or alternatively 1 to 4 carbon atoms. In any (R 4 The two Rs in the 2N) part 4 The groups can be bonded to the same nitrogen (N) atom and linked to complete a heterocycle, preferably having 5 or 6 members.

[0063] Alternatively, the phosphazene base catalyst may be a salt and have one of the following alternative chemical formulas:

[0064] [((R 42N)3P=N)p(R 4 2N) 3-p P=N(H)R 4 ] + [A - ];or

[0065] [((R 4 2N)3P=N) s (R 4 2N) 4-s P] + [A - ]

[0066] Each R 4 The phosphazene base is independently selected and as defined above, with the subscript p as defined above, the subscript s being an integer from 1 to 4, and [A] being an anion, and is generally selected from the group consisting of: fluoride, hydroxide, silanolate, alkoxy, carbonate, and bicarbonate. In one embodiment, the phosphazene base is an aminophosphazene hydroxide.

[0067] In some embodiments, the MQ resin and silane component are reacted at high temperatures, such as 75°C to 125°C, in the presence of a solvent. Suitable solvents may be hydrocarbons. Suitable hydrocarbons include aromatic hydrocarbons, such as benzene, toluene, or xylene; and / or aliphatic hydrocarbons, such as heptane, hexane, or octane. Alternatively, the solvent may be a halogenated hydrocarbon, such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride. A neutralizing agent, such as acetic acid, may be used to neutralize the catalyst after the reaction. Those skilled in the art can readily determine the catalytic amount of the catalyst to be used, which varies depending on its selection and reaction conditions. The resulting (a) polysiloxane resin can be separated or recovered from the reaction products via conventional techniques, such as stripping or other evaporation techniques.

[0068] As described above, the composition also includes (b) a photoinitiator. (b) The photoinitiator catalyzes the R in (a) the polysiloxane resin upon exposure to UV radiation. MA(b) The photoinitiator is not limited and may be selected from any known free radical photoinitiator that effectively promotes crosslinking reactions. Examples of photoinitiators include diethoxyacetophenone (DEAP), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, diethoxyflavone, chloro-thioxanone, azobisisobutyronitrile, N-methyldiethanolamine benzophenone, 4,4'-bis(dimethylamino)benzophenone, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, 1-hydroxycyclohexyl-phenyl-methyl ketone, 2-hydroxy-2-methyl-1-phenylprop-1-one, 2-methyl-1-[4-(methyl-1-ethyl-2 ... [Thio)phenyl]-2-morpholinoprop-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-prop-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)but-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-prop-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl-phenyl)but-1-one, and combinations thereof.

[0069] (b) The photoinitiator content is the effective amount for photocuring of the composition. In various embodiments, the content of (b) photoinitiator present in the composition per 100 parts by weight is from about 0.01 parts by weight to about 5 parts by weight, alternatively from about 0.1 parts by weight to about 5 parts by weight, or alternatively from about 0.1 parts by weight to about 3 parts by weight, based on the total mass of the composition.

[0070] In some embodiments, the composition further comprises (c) a functional diluent. The (c) functional diluent typically comprises a functional group selected from epoxy groups and acryloyloxy groups. Examples of epoxy groups include 3-epoxypropoxypropyl, 4-epoxypropoxybutyl, or similar epoxypropoxyalkyl groups; 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, or similar epoxycyclohexyl groups; and 4-oxacyclopropylbutyl, 8-oxacyclopropyloctyl, or similar oxacyclopropyl groups. An example of an acryloyloxy group is 3-methacryloyloxypropyl.

[0071] In some embodiments, (c) the functional diluent comprises a polyfunctional acrylate. The polyfunctional acrylate comprises two or more acryloyloxy functional groups. Examples of multifunctional acrylates include (alkyl)acrylic acid compounds having two or more acryloyloxy groups or methacryloyl groups, such as trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyoxyethylene modified trimethylolpropane tri(meth)acrylate, polyoxypropylene modified trimethylolpropane tri(meth)acrylate, polyoxyethylene / polyoxypropylene modified trimethylolpropane tri(meth)acrylate, dimethyloxetane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, phenylethylene glycol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, poly(propylene glycol) di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, di(methyl)methacrylate, etc. Neopentyl glycol acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantanediethanol di(meth)acrylate, di(meth)acrylate isophthalic acid, di(meth)acrylate isophthalic acid, di(meth)acrylate terephthalic acid, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tri(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate ) acrylates, pentaerythritol penta(meth)acrylates, pentaerythritol hexa(meth)acrylates, ethylene-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, propylene-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, ethylene / propylene-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, pentaerythritol penta / hexaacrylates, and combinations thereof.

[0072] It should be understood that the above-described (alkyl)acrylate compounds are for the sake of brevity only, based on (meth)acrylate substances, and those skilled in the art will readily understand that other alkyl and / or hydride forms of such compounds can be used equivalently. For example, those skilled in the art will understand that the monomer “(meth)acrylate 2-ethylhexyl ester” listed above exemplifies both (meth)acrylate 2-ethylhexyl ester and 2-ethylhexyl acrylate. Similarly, although acrylic monomers are generally described as acrylates (i.e., α,β-unsaturated esters) in the examples above, it should be understood that the term “acrylate” used in these descriptions can be used equivalently to the acid, salt, and / or conjugate base of the exemplified ester. For example, those skilled in the art will understand that the monomer “methyl acrylate” listed above exemplifies methyl acrylate as well as acrylic acid, acrylate salts (e.g., sodium acrylate), etc. Furthermore, multifunctional derivatives / variations of the above-described acrylic monomers can also be used. For example, the monomer “(meth)acrylate” listed above exemplifies functionalized derivatives such as substituted (meth)acrylate and ethyl acrylate (e.g., hydroxyethyl (meth)acrylate and hydroxyethyl acrylate, respectively).

[0073] In these or other embodiments, (c) the functional diluent may be selected from lower alkyl acrylates, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate; lower alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and isopropyl methacrylate; higher acrylates, such as n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, and stearyl acrylate; higher methacrylates, such as n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate. - Ethylhexyl ester, octyl methacrylate, lauryl methacrylate, stearyl methacrylate; vinyl esters of lower fatty acids, such as vinyl acetate and vinyl propionate; vinyl esters of higher fatty acids, such as vinyl butyrate, vinyl hexanoate, 2-ethylhexanoate, vinyl lauryl ester, vinyl stearate; aromatic vinyl monomers, such as styrene, vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, and vinylpyrrolidone; amino-functionalized vinyl monomers, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylaminoethyl methacrylate; amide-functionalized vinyl monomers, such as acrylamide, N- Hydroxymethylacrylamide, N-methoxymethylacrylamide, isobutoxymethoxyacrylamide, N,N-dimethylacrylamide, methacrylamide, N-hydroxymethylmethylacrylamide, N-methoxymethylmethylacrylamide, isobutoxymethoxymethacrylamide, and N,N-dimethylmethylacrylamide; hydroxyl-functionalized vinyl monomers, such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, and 2-hydroxypropyl methacrylate; fluorinated vinyl monomers, such as trifluoropropyl acrylate, perfluorobutyl acrylate, perfluorooctyl acrylate, trifluoropropyl methacrylate, and perfluorobutyl methacrylate. Perfluorooctyl ethyl methacrylate; epoxy-functionalized vinyl monomers, such as glycidyl acrylate, 3,4-epoxycyclohexyl acrylate, glycidyl methacrylate, and 3,4-epoxycyclohexyl methacrylate; ether-containing vinyl monomers, such as tetrahydrofurfuryl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, polyethylene glycol acrylate, polypropylene glycol monoacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, and polypropylene glycol monomethacrylate; alkoxysilanes containing unsaturated groups capable of free radical polymerization, such as...

[0074] ●CH2=CHCOOC3H6Si(OCH3)3,

[0075] ●CH2=C(CH3)COOC3H6Si(OCH3)3,

[0076] ●CH2=C(CH3)COOC3H6Si(CH3)(OCH3)2,

[0077] ●CH2=C(CH3)COOC3H6Si(CH3)2OCH3,

[0078] ●CH2=C(CH3)COOC2H4OC3H6Si(OCH3)3,

[0079] ●CH2=C(CH3)COOC 12 H 24 Si(OCH3)3、

[0080] ●CH2=CHOC3H6Si(CH3)(OC2H5)2,

[0081] ●CH2=CHSi(OCH3)3、

[0082] ●CH2=CHSi(OC2H5)3 and

[0083] ●CH2=CHSi(C4H9)(OC4H9)2;

[0084] Unsaturated functionalized organosilicon compounds, such as organopolysiloxanes (branched or linear) with an acryloyl or methacryloyl group at a single end and polydimethylsiloxanes with a styrene group at a single end; butadiene; vinyl chloride; vinylidene chloride; acrylonitrile and methacrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride; free radical polymerizable unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and their alkali metal salts, ammonium salts, and organic amine salts; free radical polymerizable unsaturated monomers containing sulfonic acid residues, such as styrene sulfonic acid, and their alkali metal salts, ammonium salts, and organic amine salts; quaternary ammonium salts derived from (meth)acrylic acid, such as 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride; and methacrylates of alcohols containing tertiary amine groups, such as diethylamino methacrylate, and their quaternary ammonium salts. In some embodiments, acrylate monomers, methacrylate monomers, and styrene monomers are preferred among the foregoing substances.

[0085] Also usable as (c) functional diluents are multifunctional vinyl monomers, which may be, for example, acryloyl or methacryloyl functional monomers, such as trimethylolpropane triacrylate, pentaerythritol triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane trioxyethyl acrylate, tri(2-hydroxyethyl) isocyanurate diacrylate, tri(2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, etc. Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethyl methacrylate, tri(2-hydroxyethyl) isocyanurate dimethacrylate, tri(2-hydroxyethyl) isocyanurate trimethacrylate, diacrylates and dimethacrylates of diols as adducts of ethylene oxide or propylene oxide with bisphenol A, and diacrylates and dimethacrylates of diols as adducts of ethylene oxide or propylene oxide with hydrogenated bisphenol A. Other usable polyfunctional vinyl monomers may also be, for example, triethylene glycol divinyl ether and divinylbenzene.

[0086] Alternatively or otherwise, (c) the functional diluent may comprise an organopolysiloxane having two or more acryloyloxy functional groups. Typically, the acryloyloxy functional group is at the end of the organopolysiloxane, but may be at a side-chain position. The organopolysiloxane is typically linear and may have a degree of polymerization of 1 to 1,000, alternatively 1 to 500. For example, the organopolysiloxane may be a polydimethylsiloxane terminated with a methacrylate functional group (e.g., 3-acryloyloxypropyl).

[0087] In these or other embodiments, (c) the functional diluent may be selected from silane compounds, including 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriacetoxysilane, 2-(3,4-epoxycyclohexylethyl)trimethoxysilane, and combinations thereof.

[0088] If used, (c) the functional diluent may comprise a blend of different functional diluents and is typically present in the composition in an amount greater than 0 wt% to 40 wt%, alternatively greater than 0 wt% to 30 wt%, alternatively greater than 0 wt% to 20 wt%, or alternatively 5 wt% to 15 wt%, based on the total weight of the composition.

[0089] In some embodiments, the composition further comprises (d) a condensation catalyst. The (d) condensation catalyst is used when it is desirable to dual-cur the composition during film formation, for example, by irradiation and moisture curing. The moisture used for moisture curing purposes can be ambient moisture caused by relative humidity, i.e., moisture curing does not require active introduction of moisture. However, if desired, the moisture can be selectively controlled, for example, by influencing the moisture curing rate by increasing relative humidity.

[0090] As described above, (a) polysiloxane resins include both acryloyloxy functionality and a significant SiOZ content. In contrast, conventional silicone resins containing acryloyloxy functional groups typically contain much less SiOZ and are solid at room temperature in the absence of solvents. However, the combination of acryloyloxy functionality and a significant SiOZ content in (a) polysiloxane resins allows for dual curing via irradiation and moisture. The higher SiOZ content contributes to a higher moisture-curing crosslinking density compared to conventional silicone resins with lower SiOZ content. These benefits are additional to those related to the fact that (a) polysiloxane resins are liquid at room temperature.

[0091] (d) Specific examples of condensation catalysts include organometallic catalysts, including titanium compounds such as tetra(isopropoxy)titanium, tetra(n-butoxy)titanium, tetra(tert-butoxy)titanium, di(isopropoxy)bis(ethyl acetoacetate)titanium, di(isopropoxy)bis(methyl acetoacetate)titanium and di(isopropoxy)bis(acetylacetonate)titanium, etc.; zirconium compounds such as tetra(isopropoxy)zirconium, tetra(n-butoxy)zirconium, tetra(tert-butoxy)zirconium, di(isopropoxy)bis(ethyl acetoacetate)zirconium, di(isopropoxy)bis(methyl acetoacetate)zirconium and di(isopropoxy)bis(acetylacetonate)zirconium, etc.; tin compounds such as dimethyltin dinedecanoate, dibutyltin dilaurate, dibutyltin dioctanoate, etc.; and stannous octoate, etc.

[0092] When used, the content of (d) condensation catalyst is an effective amount for moisture curing. In various embodiments, the content of (d) condensation catalyst present in every 100 parts by weight is from about 0.01 parts by weight to about 10 parts by weight, optionally from about 0.05 parts by weight to about 10 parts by weight, or optionally from about 0.05 parts by weight to about 5 parts by weight, based on the total mass of the composition.

[0093] The composition may optionally further comprise additive components. Additive components may be selected from plasticizers, surface modifiers, waxes, reinforcing agents, dyes, pigments, colorants, fillers, flame retardants, release agents, antioxidants, compatibilizers, UV stabilizers, thixotropic agents, anti-aging agents, lubricants, coupling agents, solvents or carrier media, rheology accelerators, adhesion accelerators, thickeners, and combinations thereof.

[0094] One or more of the additives may be present in any suitable weight percentage (wt%) of the composition, such as 0.1 wt% to 15 wt%, 0.5 wt% to 5 wt%, or 0.1 wt% or less, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, or 15 wt% or more. Those skilled in the art can readily determine the appropriate amount of the additive based on, for example, the type of additive and the desired results. Certain optional additives are described in more detail below.

[0095] A suitable carrier medium can be considered a solvent when it is capable of dissolving the components of the composition. Suitable carrier media include organosilicones (linear and cyclic), organic oils, organic solvents, water (where the composition is used as an oil-in-water emulsion), and mixtures thereof. Specific examples of organic solvents include hydrocarbons, such as aromatics including benzene, toluene, or xylene, and aliphatic hydrocarbons such as heptane, hexane, or octane.

[0096] In a specific embodiment, the composition is substantially free of, and optionally free of, carrier media and / or solvents. "Substantially free of" means that, based on the total weight of the composition, the composition contains less than 5% by weight, optionally less than 4% by weight, optionally less than 3% by weight, optionally less than 2% by weight, optionally less than 1% by weight, and optionally 0% by weight of carrier media and / or solvents. For the purposes of this disclosure, (c) functional diluents optionally included in the composition are not considered carrier media or solvents, even if the use of (c) functional diluents reduces the viscosity of the composition. In one specific embodiment, the composition is free of organic solvents.

[0097] The composition may contain one or more fillers. The fillers may be one or more reinforcing fillers, unreinforcing fillers, or mixtures thereof. Examples of finely pulverized reinforcing fillers include high surface area fumed and precipitated silica, comprising rice husk ash and a certain degree of calcium carbonate. Pyrolytic silica may include surface functionalizations, such as hydrophilic or hydrophobic, and is available from Cabot Corporation under the trade name CAB-O-SIL. Examples of finely pulverized unreinforcing fillers include pulverized quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide and carbon black, talc, and calcium silicate. Other fillers that may be used alone or in addition to those described above include carbon nanotubes such as multi-walled carbon nanotube bauxite, hollow glass spheres, alumina, calcium sulfate (anhydrite), gypsum, calcium sulfate, magnesium carbonate, clays such as kaolin, alumina trihydrate, magnesium hydroxide (brucite), graphite, copper carbonate such as malachite, nickel carbonate such as zarachite, barium carbonate such as barite, and / or strontium carbonate such as strontium sappanite. Other alternative fillers include alumina, selected from silicates such as olivine, garnet, aluminosilicates, cyclosilicates, chain silicates, and lamellar silicates. In some embodiments, the composition comprises at least one filler comprising hollow particles, such as hollow spheres. When used, the filler may be used in the composition in amounts from 0.01 wt% to 50 wt%, alternatively from 0.05 wt% to 40 wt%, or alternatively from 0.1 wt% to 35 wt%, based on the total weight of the composition. Furthermore, the amount of pyrolytic silica (if used) may be from 0.01 wt% to 5 wt%, alternatively from 0.05 wt% to 3 wt%, alternatively from 0.1 wt% to 2.5 wt%, or alternatively from 0.2 wt% to 2.2 wt%, based on the total weight of the composition.

[0098] The filler (if used) may optionally be surface-treated with a treatment agent. Treatment agents and methods are understood in the art. Surface treatment of the filler is typically performed, for example, with fatty acids or fatty acid esters such as stearates or with organosilanes, organosiloxanes, or organosilazanes such as hexaalkyldisilazanes or short-chain siloxane diols. Generally, surface treatment renders one or more fillers hydrophobic, and thus easier to process and obtain a homogeneous mixture with the other components in the composition. Silanes such as R... 4 e Si(OR 5 ) 4-e It can also be used as a treatment agent for fillers, wherein R 4 A monovalent hydrocarbon group consisting of 6 to 20 carbon atoms, either substituted or unsubstituted, such as alkyl groups including hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, and aralkyl groups including benzyl and phenethyl. 5 It is an alkyl group with 1 to 6 carbon atoms, and the subscript e is equal to 1, 2 or 3.

[0099] In various embodiments, the composition further comprises an adhesion promoter. The adhesion promoter can improve the adhesion of the foam to the substrate material it contacts during curing. In some embodiments, the adhesion promoter is selected from organosilicon compounds having at least one alkoxy group bonded to a silicon atom in the molecule. Examples of such alkoxy groups are methoxy groups, ethoxy groups, propoxy groups, butoxy groups, and methoxyethoxy groups. Furthermore, examples of non-alkoxy groups bonded to the silicon atoms of the organosilicon compound include: substituted or unsubstituted monovalent hydrocarbon groups, such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups, haloalkyl groups, etc.; epoxy-containing monovalent organic groups, such as 3-epoxypropoxypropyl groups, 4-epoxypropoxybutyl groups or similar epoxypropoxyalkyl groups; 2-(3,4-epoxycyclohexyl)ethyl groups, 3-(3,4-epoxycyclohexyl)propyl groups or similar epoxycyclohexyl groups; and 4-oxacyclopropanebutyl groups, 8-oxacyclopropaneoctyl groups or similar oxacyclopropane groups; monovalent organic groups containing acrylate groups, such as 3-methacryloyloxypropyl groups; and hydrogen atoms.

[0100] These organosilicon compounds typically possess silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms. Furthermore, due to their ability to impart good adhesion to various types of matrix materials, these organosilicon compounds typically have at least one monovalent organic group containing an epoxy group in the molecule. Examples of this type of organosilicon compound are organosilane compounds, organosiloxane oligomers, and alkyl silicate esters. Examples of the molecular structures of organosiloxane oligomers or alkyl silicate esters include linear structures, partially branched linear structures, branched structures, cyclic structures, and network structures. Linear, branched, and network structures are typical. Examples of this type of organosilicon compound include: silane compounds, such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, etc.; siloxane compounds having at least one silicon-bonded alkenyl group or a silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy group in the molecule; silane compounds having at least one silicon-bonded alkoxy group or mixtures of siloxane compounds with at least one silicon-bonded hydroxyl group and at least one silicon-bonded alkenyl group in the molecule; and methyl polysilicates, ethyl polysilicates and ethyl polysilicates containing epoxy groups.

[0101] In some embodiments, the composition comprises essentially the following, and alternatively the following: (a) a polysiloxane resin, (b) a photoinitiator and optionally (c) a functional diluent, optionally (d) a condensation catalyst and optionally a filler.

[0102] The viscosity of the composition at 25°C is typically greater than 0 cp to 50,000 cp, alternatively 100 cp to 20,000 cp, alternatively 200 cp to 10,000 cp, alternatively 200 cp to 5,000 cp, and alternatively 200 cp to 1,000 cp, even in the absence of any solvent or carrier. Therefore, the composition is flowable at room temperature and can form uniform coatings and films.

[0103] The composition can be used in a variety of end-use applications. For example, the composition can be used to form films with excellent physical properties, including scratch resistance. These films can be used in electronic applications (e.g., as protective or conformal coatings), waveguides, and as protective coatings (e.g., for windows or displays or other easily scratched substrates). The film can also be patterned, for example, by using selective curing with a photomask.

[0104] As described above, a method for preparing a film using a composition includes applying the composition onto a substrate to obtain an uncured layer. The method further includes irradiating the uncured layer to obtain the film. When the composition contains (d) a condensation catalyst, the method may also include moisture curing of the uncured layer and / or the film.

[0105] The composition can be applied to the substrate in any suitable manner (i.e., set or dispensed). Typically, the composition is applied in wet form using a wet coating technique. The composition can be applied by: i) spin coating; ii) brush coating; iii) drop coating; iv) spray coating; v) dip coating; vi) roll coating; vii) flow coating; viii) trench coating; ix) concave coating; x) Myer bar coating; or xi) any combination of two or more of i) to x). Generally, setting the composition on the substrate results in a wet deposit or uncured layer on the substrate, which is then cured to obtain a film on the substrate.

[0106] The substrate is unrestricted and can be any substrate. The film can be separated from the substrate, or it can be physically and / or chemically bonded to the substrate, depending on the choice. The substrate may optionally have continuous or discontinuous shapes, sizes, dimensions, surface roughness, and other properties.

[0107] The substrate may be an electronic article or component. In other embodiments, the substrate may include glass. Alternatively, the substrate may include plastic, which may be thermosetting and / or thermoplastic. However, alternatively, the substrate may be or comprise metal, ceramic, glass fiber, cellulose (e.g., paper), wood, cardboard, paperboard, silicone, or polymer materials, or combinations thereof.

[0108] Specific examples of suitable substrates include paper blanks, such as kraft paper, polyethylene-coated kraft paper (PEK coated paper), thermal paper, and conventional paper; polymer substrates, such as polyamide (PA); polyesters, such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polypropylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins, such as polyethylene (PE), polypropylene (PP), and polybutene; styrene-based resins; polyoxymethylene (POM); polycarbonate (PC); polymethyl methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); and poly... Phenyl ether (PPE); polyimide (PI); polyamide-imide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone; polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); polyether nitrile (PEN); phenolic resins; phenoxy resins; cellulose, such as triacetyl cellulose, diacetyl cellulose and cellophane; fluorinated resins, such as polytetrafluoroethylene; thermoplastic elastomers, such as polystyrene-type, polyolefin-type, polyurethane-type, polyester-type, polyamide-type, polybutadiene-type, polyisoprene-type and fluorinated types; and copolymers and combinations thereof.

[0109] Wet deposits or uncured layers are cured by exposure to irradiation (typically UV radiation). Available UV radiation sources include conventional mercury vapor lamps (designed to emit UV energy across a wide range of wavelengths), LED curing lamps, and more. For example, available radiation wavelengths range from 200 nm to 400 nm. UV curing typically operates at 40 milliwatts per centimeter. 2 ("mW / cm" 2 (Up to 30,000 mW / cm) 2 Within a range, such as approximately 70 mW / cm 2 Approximately 300 mW / cm 2 This is achieved within a certain range. In some embodiments, the irradiation is carried out in an inert atmosphere, such as under nitrogen.

[0110] If desired, the film formed by irradiating the uncured layer can be patterned. For example, in these embodiments, a photomask is typically used in the selective curing of target portions of the uncured layer. The photomask typically has a defined pattern for transmitting UV radiation and a complementary pattern for blocking UV radiation transmission. For example, the photomask includes portions that allow UV radiation transmission and portions that block UV radiation transmission, such that the defined pattern can be transferred or replicated via selective curing. The UV-transmitting portions of the photomask are aligned with the target portions of the uncured layer, while the complementary portions that block UV radiation transmission are aligned with the non-target portions of the uncured layer. Such a method may be called photolithography. The target portions of the uncured layer are cured to provide cured areas, and the non-target portions of the uncured layer are not cured to provide uncured areas.

[0111] Uncured areas of a film retained by using a photomask can be etched using wet methods (e.g., with organic solvents or aqueous alkalis), or alternatively, dry methods (e.g., with plasma or reactive ions). Typically, uncured areas are etched or removed using solvents such as butyl acetate, alcohols, ketones, aromatics, alkanes, ethers, esters, and combinations thereof. Etching or removing uncured areas produces only cured areas, which can have 100% pattern retention.

[0112] When the composition contains (d) a condensation catalyst and the method further includes moisture curing of the composition (and / or the film formed by irradiation), moisture curing can be carried out without any pretreatment steps. The composition (and / or the film formed by irradiation) can be moisture cured before, during, or after irradiation curing. In one embodiment, moisture curing is effective after irradiation curing by removing the inert atmosphere and exposing the film formed by irradiation to moisture (e.g., relative humidity). When irradiation is performed in an inert atmosphere, sequential curing steps are typically used, and the inert atmosphere typically does not contain ambient moisture that would affect moisture curing.

[0113] In some embodiments, the membrane may be exposed to post-baking, for example, to an elevated temperature for a period of time. The elevated temperature is typically 80°C to 140°C, or alternatively 100°C to 120°C.

[0114] The coated substrate (which includes a film formed from the composition on the substrate) can have different dimensions, including the relative thickness of the film and the substrate. The thickness of the film can vary depending on its end-use application. The film thickness can be greater than 0 μm to 4,000 μm, alternatively greater than 0 μm to 3,000 μm, alternatively greater than 0 μm to 2,000 μm, alternatively greater than 0 μm to 1,000 μm, alternatively greater than 0 μm to 500 μm, alternatively greater than 0 μm to 250 μm. However, other thicknesses are conceivable, for example, from 0.1 μm to 200 μm. For example, the film thickness can be from 0.2 μm to 175 μm; alternatively from 0.5 μm to 150 μm; alternatively from 0.75 μm to 100 μm; alternatively from 1 μm to 75 μm; alternatively from 2 μm to 60 μm; alternatively from 3 μm to 50 μm; and alternatively from 4 μm to 40 μm. Alternatively, when the substrate is plastic, the film thickness can be greater than 0 μm to 200 μm, alternatively greater than 0 μm to 150 μm, and alternatively greater than 0 μm to 100 μm.

[0115] If desired, the membrane may be subjected to further processing depending on its end-use application. For example, the membrane may undergo oxidation deposition (e.g., SiO2 deposition), resist deposition, and patterning, etching, chemical, corona, or plasma stripping, metallization, or metal deposition. Such further processing techniques are generally known. This deposition can be chemical vapor deposition (including low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and plasma-assisted chemical vapor deposition), physical vapor deposition, or other vacuum deposition techniques. Many of these further processing techniques involve elevated temperatures, particularly vacuum deposition, which is well-suited to membranes due to their excellent thermal stability. However, depending on the membrane's end-use, the membrane may be used in conjunction with such further processing.

[0116] The following examples are intended to illustrate the invention and should not be construed in any way as limiting the scope of the invention. Some of the components used in the examples are shown in Table 1 below, followed by the characterization and evaluation procedures also used in the examples.

[0117] Table 1 – Components

[0118] MQ resin <![CDATA[Formula ((CH3)3SiO 1 / 2 ) 43.2 (HOSiO 3 / 2 ) 11.5 (SiO 4 / 2 ) 45.3 of the solid resin powder]]> Silane compounds (1) (3-Methacryloxypropyl)trimethoxysilane Silane compounds (2) dimethyldimethoxysilane Silane compounds (3) (3-Methyloxypropyl)methyldimethoxysilane catalyst KOH Neutralizing agent Acetic acid Solvent (1) <![CDATA[Toluene (C7H8)]]> W <![CDATA[(CH3)3SiO 1 / 2 ]]> <![CDATA[X MA ]]> <![CDATA[[MeR MA SiO 1 / 2 (OZ)] and [MeR MA SiO 2 / 2 ]]]> X <![CDATA[[Me2SiO 1 / 2 (OZ)] and [Me2SiO] 2 / 2 ]]]> Y <![CDATA[[MeSiO 3 / 2 , [MeSiO 2 / 2 (OZ)], and [MeSiO 1 / 2 (OZ)2]]]> <![CDATA[Y MA ]]> <![CDATA[[R MA SiO 3 / 2 , [R MA SiO 2 / 2 (OZ)] and [R MA SiO 1 / 2 (OZ)2]]]> Z <![CDATA[[SiO 1 / 2 (OZ)3], [SiO 2 / 2 (OZ)2], [SiO 3 / 2 (OZ)], and [SiO 4 / 2 > OZ OH or OMe Photoinitiator (1) 2,2-Dimethoxy-1,2-diphenylethyl-1-one Photoinitiator (2) 2-Hydroxy-2-methyl-1-phenyl-prop-1-one Photoinitiator (3) 2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one Condensation catalyst Tetraisopropyl titanate Functional diluent (1) Tri(propylene glycol) diacrylate Functional diluent (2) Trimethylolpropane triacrylate Functional diluents (3) Dipentaerythritol penta / hexaacrylate Functional diluents (4) A formylpropyl-terminated polydimethylsiloxane with a viscosity of 50-90 cst at 25°C filler Colloidal silica (30% by weight in methyl ethyl ketone)

[0119] Nuclear magnetic resonance spectroscopy (NMR)

[0120] Nuclear magnetic resonance (NMR) spectra were obtained using a Varian EX-400 5MHz Mercury spectrometer with CDCl3 solvent. 1 H-NMR, 13 C-NMR and 29The chemical shift of the Si-NMR spectrum references the internal solvent resonance and is reported relative to tetramethylsilane.

[0121] Gel permeation chromatography (GPC)

[0122] Gel permeation chromatography (GPC) analysis was performed on an Agilent 1260 Infinity II system equipped with a triple detector consisting of a differential refractometer, an online differential viscometer, small-angle light scattering (LALS: detection angles of 15° and 90°), and a column (2PL gel-mix C, Varian). Toluene (HPLC grade, Biosolve) was used as the mobile phase at a flow rate of 1 mL / min.

[0123] Dynamic viscosity (DV)

[0124] Dynamic viscosity (DV) was measured using a Brookfield DV-III Ultra programmable rheometer equipped with a CPA-52Z rotor at a temperature of 25°C with a sample volume of 0.5 mL.

[0125] SiO2 content

[0126] The SiOZ content can be determined by... 29 The calculations were performed using Si-NMR. Specifically, the molar content of the following silanoxy units in each polysiloxane resin was determined:

[0127] M=R'3SiO 1 / 2

[0128] D1=R'2(OZ)SiO 1 / 2

[0129] D2=R'2SiO 2 / 2

[0130] T1=R'(OZ)2SiO 1 / 2

[0131] T2=R'(OZ)SiO 2 / 2

[0132] T3=R'SiO 3 / 2

[0133] Q1=(OZ)3SiO 1 / 2

[0134] Q2=(OZ)2SiO 2 / 2

[0135] Q3=(OZ)SiO 3 / 2

[0136] Q4 = SiO 4 / 2

[0137] The OZ content relative to silicon atoms in mol% can be calculated using the following formula, where the label of each peak corresponds to the area of ​​integration under that labeled peak:

[0138]

[0139] In the examples, R' is a methyl or acryloyloxy functional group.

[0140] Preparation Example 1: Polysiloxane Resin (A1)

[0141] 800 g of solvent (1), followed by 500 g of MQ resin, was placed in a 3 L flask equipped with a magnetic stir bar. 340 g of silane compound (1) and 0.82 g of catalyst were added to the flask. The contents of the flask were refluxed under nitrogen (70 °C) with stirring, and the reaction progress was monitored by GC. After 4 hours, the contents of the flask were cooled to 23 °C, and 1.23 g of neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 μm filter to obtain a clear and viscous liquid. The polysiloxane resin (A1) was separated from the reaction product by removing volatiles using a rotary evaporator. The polysiloxane resin (A1) was analyzed and characterized in Table 2 below.

[0142] Preparation Example 2: Polysiloxane Resin (A2)

[0143] 800 g of solvent (1), followed by 500 g of MQ resin, was placed in a 3 L flask equipped with a magnetic stir bar. 340 g of silane compound (1) and 0.82 g of catalyst were added to the flask. The contents of the flask were refluxed under nitrogen (70 °C) with stirring, and the reaction progress was monitored by GC. After confirming that silane compound (1) had been consumed (by GC), 18.4 g of water and 20 g of methanol were added to the flask, and a Dean-Stark head was attached to it. The contents of the flask were stirred and heated to 95 °C, while collecting the volatiles and replacing the collected volume of volatiles with solvent (1). After reaching 95 °C, the contents of the flask were cooled to 23 °C, and 1.23 g of neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 μm filter to obtain a clear and viscous liquid. Polysiloxane resin (A2) was separated from the reaction products by removing volatiles using a rotary evaporator. The polysiloxane resin (A2) was analyzed and characterized in Table 2 below.

[0144] Preparation Example 3: Polysiloxane Resin (A3)

[0145] 800 g of solvent (1), followed by 500 g of MQ resin, was placed in a 3 L flask equipped with a magnetic stir bar. 340 g of silane compound (1) and 0.82 g of catalyst were added to the flask. The contents of the flask were refluxed under nitrogen (70 °C) with stirring, and the reaction progress was monitored by GC. After confirming that silane compound (1) had been consumed (by GC), 18.4 g of water and 20 g of methanol were added to the flask, and a Dean-Stark head was attached to it. The contents of the flask were stirred and heated to 102 °C, while collecting the volatiles and replacing the collected volume of volatiles with solvent (1). After reaching 102 °C, the contents of the flask were cooled to 23 °C, and 1.23 g of neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 μm filter to obtain a clear and viscous liquid. Polysiloxane resin (A3) was separated from the reaction products by removing volatiles using a rotary evaporator. The polysiloxane resin (A3) was analyzed and characterized in Table 2 below.

[0146] Example 4: Polysiloxane resin (A4)

[0147] 800 g of solvent (1), followed by 506 g of MQ resin, was placed in a 3 L flask equipped with a magnetic stir bar. 340 g of silane compound (1) and 0.82 g of catalyst were added to the flask. The contents of the flask were refluxed under nitrogen (70 °C) with stirring, and the reaction progress was monitored by GC. After 5.5 hours, the contents of the flask were cooled to 23 °C, and 1.23 g of neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 μm filter to obtain a clear and viscous liquid. The polysiloxane resin (A4) was separated from the reaction product by removing volatiles using a rotary evaporator. The polysiloxane resin (A4) was analyzed and characterized in Table 2 below.

[0148] Example 5: Polysiloxane resin (A5)

[0149] 500 g of solvent (1), followed by 300 g of MQ resin, was placed in a 2 L flask equipped with a magnetic stir bar. 152 g of silane compound (1), 49 g of silane compound (2), and 0.30 g of catalyst were added to the flask. The contents of the flask were refluxed under nitrogen (70 °C) with stirring, and the reaction progress was monitored by GC. After 6 hours, the contents of the flask were cooled to 23 °C, and 0.45 g of neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 μm filter to obtain a clear and viscous liquid. The polysiloxane resin (A5) was separated from the reaction product by removing volatiles using a rotary evaporator. The polysiloxane resin (A5) was analyzed and characterized in Table 2 below.

[0150] Example 6: Polysiloxane resin (A6)

[0151] 500 g of solvent (1), followed by 300 g of MQ resin, was placed in a 2 L flask equipped with a magnetic stir bar. 152 g of silane compound (1), 49 g of silane compound (2), and 0.30 g of catalyst were placed in the flask. The contents of the flask were refluxed under nitrogen (70 °C) with stirring, and the reaction progress in the flask was monitored by GC. After confirming that silane compounds 1 and 2 had been consumed (by GC), 11 g of water and 20 g of methanol were placed in the flask, and a Dean-Stark head was attached to it. The contents of the flask were stirred and heated to 105 °C, while collecting the volatiles and replacing the collected volatiles with the volume of solvent (1). After reaching 105 °C, the contents of the flask were cooled to 23 °C, and 0.45 g of neutralizing agent was placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 μm filter to obtain a clear and viscous liquid. Polysiloxane resin (A6) was separated from the reaction products by removing volatiles using a rotary evaporator. The polysiloxane resin (A6) was analyzed and characterized in Table 2 below.

[0152] Example 7: Polysiloxane resin (A7)

[0153] 200 g of solvent (1), followed by 100 g of MQ resin, was placed in a 1 L flask equipped with a magnetic stir bar. 50.7 g of silane compound (1), 31.6 g of silane compound (3), and 0.10 g of catalyst were added to the flask. The contents of the flask were refluxed under nitrogen (70 °C) with stirring, and the reaction progress was monitored by GC. After 10 hours, the contents of the flask were cooled to 23 °C, and 0.15 g of neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 μm filter to obtain a clear and viscous liquid. The polysiloxane resin (A7) was separated from the reaction product by removing volatiles using a rotary evaporator. The polysiloxane resin (A7) was analyzed and characterized in Table 2 below.

[0154] Example 8: Polysiloxane resin (A8)

[0155] 200 g of solvent (1), followed by 100 g of MQ resin, was placed in a 1 L flask equipped with a magnetic stir bar. 50.7 g of silane compound (1), 31.6 g of silane compound (3), and 0.10 g of catalyst were placed in the flask. The contents of the flask were refluxed under nitrogen (70 °C) with stirring, and the reaction progress in the flask was monitored by GC. After confirming that silane compounds 1 and 3 had been consumed (by GC), 3.7 g of water and 10 g of methanol were placed in the flask, and a Dean-Stark head was attached to it. The contents of the flask were stirred and heated to 105 °C, while collecting the volatiles and replacing the collected volatiles with solvent (1). After reaching 105 °C, the contents of the flask were cooled to 23 °C, and 0.15 g of neutralizing agent was placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 μm filter to obtain a clear and viscous liquid. The polysiloxane resin (A8) was separated from the reaction products by removing volatiles using a rotary evaporator. The polysiloxane resin (A8) was analyzed and characterized in Table 2 below.

[0156] pass 29 The polysiloxane resins prepared in Examples 1-8 above were analyzed by Si-NMR, GPC, and DV. The results are shown in Table 2 below.

[0157] Table 2 :

[0158]

[0159] Examples 1-24 and Comparative Examples 1-2

[0160] Compositions were prepared using polysiloxane resins (A1)-(A8). The components and relative amounts used in each of Examples 1-24 and Comparative Examples 1-2 are shown in Table 3 below. In Table 3, the specific substances (based on Table 1) of the polysiloxane resins, photoinitiators, and functional diluents used are determined. For example, for the photoinitiator, “(1) 2.0” indicates that photoinitiator (1) is 2 grams. In Table 3, CE indicates a comparative example. Each composition was prepared by placing the components in an amber dental mixing cup and mixing.

[0161] Table 3 :

[0162]

[0163] The compositions of Examples 1-24 and Comparative Examples 1-2 were used to prepare films. Specifically, each composition was applied to a glass substrate using a doctor blade to form a 250-micrometer thick coating. Each coating was then exposed to UV radiation (0.5 joule dose broadband) at 23°C under nitrogen atmosphere using a Fusion Systems Corporation Model 31983-E instrument to obtain a cured film. Each cured film was then analyzed; if it was liquid or tacky to the touch, it was considered "unacceptable." If the cured film was non-liquid and not tacky to the touch, it was considered "acceptable" (reported in Table 4 below).

[0164] Some films formed using the compositions of Examples 1-24 and Comparative Examples 1-2 were double-cured by moisture curing after the above-described UV curing step. For those double-cured coatings, the cured films (on a glass substrate) formed after exposure to UV radiation were placed in an environment of 23°C and 50% relative humidity. For those coatings that were not double-cured, the uncured layer was placed on a glass substrate in an environment of 23°C and 50% relative humidity to measure the surface curing time. The surface curing time was recorded based on the time it took for the sample to form a surface layer. Cured films with a surface curing time of less than 4 hours were considered “acceptable,” and cured films without a surface layer or with a surface curing time of more than 4 hours were considered “unacceptable” (reported in Table 4 below). The surface curing time was measured in conjunction with moisture curing. Therefore, for films that were only UV-cured and not double-cured, the surface curing time was measured separately based on moisture curing in the absence of any UV curing. The last column in Table 4 regarding whether the film was UV-cured or double-cured relates to pencil hardness and adhesion values ​​(described below), but not to surface curing time.

[0165] The pencil hardness values ​​of cured films were analyzed according to ASTM D3363-05. For those cured films formed solely by exposure to UV radiation, pencil hardness was measured after UV curing. For those cured films that underwent double curing, pencil hardness was measured six days after UV curing followed by moisture curing. The results of the pencil hardness tests are listed in Table 4 below.

[0166] According to ASTM D3359, the adhesion of cured films to glass was analyzed using the Gardco PA-2000 Adhesion Test Kit. For cured films formed solely by exposure to UV radiation, adhesion to glass was measured after UV curing. For cured films that underwent double curing, adhesion to glass was measured after six days of moisture curing. The results of the pencil hardness test are listed in Table 4 below. The adhesion analysis to glass involved cross-hatching the cured films. A rating of "1" indicates poor adhesion, with more than 50% of the cured film removed. A rating of "2" indicates moderate adhesion, with 5% to 50% of the cured film removed. A rating of "3" indicates good adhesion, with less than 5% of the cured film removed.

[0167] Table 4 :

[0168]

[0169]

[0170] *Surface curing time based on moisture curing

[0171] Example 25

[0172] In Example 25, a patterned film was prepared. First, a composition was prepared by combining 8.8 g of polysiloxane resin (A1), 1.0 g of functional diluent (1), 0.2 g of photoinitiator (1), 0.3 g of silane compound (1), and 9.7 g of propylene glycol methyl ether acetate. The composition was mixed and passed through a 0.2 μm filter to remove solids and obtain a solution. The solution was spin-coated onto a 4” silicon wafer using a Karl Suss CT62 spin coater to form a coating on the silicon wafer. The silicon wafer and coating were pre-baked at 110°C for 60 seconds using a rapid thermal processing (RTP) oven with nitrogen purging, and then placed in a mask aligner equipped with a photomask with a 5–100 μm line / pitch. The coating on the silicon wafer was exposed to nitrogen at a dose of 1.0 J / cm². 2 A broadband UV source (200nm-380nm) was used, followed by exposure at 110°C on a hot plate and baking for 60 seconds to form a partially cured film on a silicon wafer. This partially cured film consisted of cured and uncured portions. The partially cured film on the silicon wafer was then immersed in butyl acetate at room temperature for 60 seconds to remove the uncured portions and form a patterned film corresponding to the photomask negative. Microscopic examination of the patterned film revealed a line / spacing pattern with 5μm resolution and 100% pattern retention.

[0173] Example 26

[0174] In Example 26, a patterned film was prepared. First, a composition was prepared by combining 8.8 g of polysiloxane resin (A5), 1.0 g of functional diluent (2), 0.2 g of photoinitiator (1), 0.3 g of silane compound (1), and 9.7 g of propylene glycol methyl ether acetate. The composition was mixed and passed through a 0.2 μm filter to remove solids and obtain a solution. The solution was spin-coated onto a 4” silicon wafer using a Karl Suss CT62 spin coater to form a coating on the silicon wafer. The silicon wafer and coating were pre-baked at 110°C for 60 seconds using a rapid thermal processing (RTP) oven with nitrogen purging, and then placed in a mask aligner equipped with a photomask with a 5–100 μm line / pitch. The coating on the silicon wafer was exposed to nitrogen at a dose of 1.0 J / cm². 2 A broadband UV source (200nm-380nm) was used, followed by exposure at 110°C on a hot plate and baking for 60 seconds to form a partially cured film on a silicon wafer. This partially cured film consisted of cured and uncured portions. The partially cured film on the silicon wafer was then immersed in butyl acetate at room temperature for 60 seconds to remove the uncured portions and form a patterned film corresponding to the photomask negative. Microscopic examination of the patterned film revealed a line / spacing pattern with 5μm resolution and 100% pattern retention.

[0175] Definition and usage of terms

[0176] The abbreviations used in this instruction manual have the definitions in Table 5 below.

[0177] Table 5 - Abbreviations

[0178] cP centipo d sky Da Dalton DP Degree of aggregation FTIR Fourier transform infrared spectroscopy g gram GC Gas chromatography GPC Gel permeation chromatography HPLC High performance liquid chromatography Me methyl mg mg MHz megahertz mL milliliters mm millimeters Mn Number-average molecular weight as measured by GPC Mp Peak molecular weight measured by GPC mPa·s millipascal second MS mass spectrometry Mw Weight-average molecular weight Mz Z-average molecular weight NMR Nuclear magnetic resonance OD outer diameter PDI polydispersity index Ph Phenyl ppm One million portions PTFE polytetrafluoroethylene RH relative humidity RT 25℃ room temperature s Second SiH content <![CDATA[As measured by 29 Si NMR, such as hydrogen bonded to silicon,]]> THF Tetrahydrofuran μL microliter μm micrometer Vi vinyl

[0179] It should be understood that the appended claims are not limited to the specific and particular compounds, compositions or methods described in the detailed embodiments, and may vary among specific embodiments falling within the scope of the appended claims.

Claims

1. A method for preparing a membrane, the method comprising: The composition is applied to a substrate to obtain an uncured layer; Irradiate the uncured layer; as well as The uncured layer is exposed to moisture to prepare the film; The composition said composition comprises: (a) a polysiloxane resin, wherein the (a) polysiloxane resin comprises the following silanoxy group: [R3SiO 1 / 2 ]、[(OZ) q SiO (4-q) / 2 And at least one of the following: [(OZ)] t R MA SiO (3-t) / 2 [] or [(OZ)] d RR MA SiO (2-d) / 2 ]; where: each R is independently a substituted or unsubstituted hydrocarbon group, each R MA Each Z is independently an acryloyloxy functional group, each Z is independently an H or alkyl group, the subscript q is a number selected from the range of 0-3 each time it appears, the subscript t is a number selected from the range of 0-2 each time it appears, and the subscript d is a number selected from the range of 0-1 each time it appears, provided that the average concentration of the OZ group is at least 12 mol% relative to the number of moles of silicon atoms in the (a) polysiloxane resin; (b) Photoinitiator; optional (c) Functional diluents; and (d) Condensation catalyst.

2. The method according to claim 1, wherein, based on the total weight of the composition, the composition contains less than 30% by weight of liquid components other than (a), (b) and (c).

3. The method according to claim 1 or 2, wherein: (i) the (a) polysiloxane resin is liquid at 25°C in the absence of any solvent; (ii) the composition is free of any solvent; or (iii) both (i) and (ii).

4. The method according to claim 1 or 2, wherein the (c) functional diluent is present in the composition, and wherein the (c) functional diluent is epoxy and / or acryloyloxy functional.

5. The method of claim 4, wherein the (c) functional diluent is present, and wherein the (c) functional diluent comprises a polyfunctional acrylate compound.

6. The method according to claim 1 or 2, wherein each R MA Independently possessing the following formula: Where X is a covalent bond or a divalent linker, and R 1 It is an H or alkyl group.

7. The method according to claim 1 or 2, further comprising disposing a photomask on the composition before and / or during curing, such that the film comprises a patterned film including cured regions and uncured regions.

8. The method of claim 7, further comprising removing the uncured areas from the patterned film using a solvent.

9. The method according to claim 1 or 2, the method further comprising (a) by causing SiO to be contained in 4 / 2 The (a) polysiloxane resin is prepared by reacting an organosilicon resin with a silane component containing a silane compound in the presence of a catalyst to obtain the (a) polysiloxane resin. The silane compound described herein has the formula R MA R 2 x Si(OR 2 ) 3-x , where each R MA Independently acryloyloxy functional group, each R 2 It is an independently chosen alkyl group having 1 to 4 carbon atoms, and the subscript x is 0 or 1.

10. A membrane formed according to the method of claim 1 or 2.

11. A composition comprising: (a) a polysiloxane resin, wherein the (a) polysiloxane resin comprises the following silanoxy group: [R3SiO 1 / 2] [(OZ)] q SiO (4-q) / 2 And at least one of the following: (OZ) t R MA SiO (3-t) / 2 [] or [(OZ)] d RR MA SiO (2-d) / 2 ];in: Each R is independently a substituted or unsubstituted hydrocarbon group, each R MA Each Z is independently an acryloyloxy functional group, each Z is independently an H or alkyl group, the subscript q is a number selected from the range of 0-3 each time it appears, the subscript t is a number selected from the range of 0-2 each time it appears, and the subscript d is a number selected from the range of 0-1 each time it appears, provided that the average concentration of the OZ group is at least 12 mol% relative to the number of moles of silicon atoms in the (a) polysiloxane resin; (b) a photoinitiator; optionally (c) a functional diluent; and (d) Condensation catalyst.

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