Method for preparing a film and composition therefor

Abstract

The method of preparing a film includes applying the composition onto a substrate to obtain an uncured layer. The method further includes irradiating the uncured layer to obtain a film. The composition includes (a) a polysiloxane resin, (b) a photoinitiator, and optionally (c) a functional diluent. The (a) polysiloxane resin includes an acryloxy functional group and an average concentration of OZ groups of at least 12 mole percent relative to the moles of silicon atoms in the (a) polysiloxane resin, where Z is independently H or an alkyl group.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority and all advantages of U.S. Provisional Patent Application No. 63 / 126,727, filed December 17, 2020, the contents of which are incorporated herein by reference.

[0002] (Field of Invention) This disclosure relates, in general, to a method for preparing a film, and more specifically, to a method for preparing a film via irradiation and to compositions therefor. [Background technology]

[0003] Silicone resins are well known in the art and are used in a variety of end applications. Silicone resins typically have T siloxy units (R 0 SiO 3 / 2 ), and / or Q siloxy units (SiO 4 / 2 )[where R 0 The three-dimensional network is due to the presence of substituents. The properties of silicone resins vary, in particular, depending on the crosslinking density and the mole fraction of siloxy units. Increasing the crosslinking density generally results in greater hardness and / or stiffness.

[0004] Silicone resins are often functionalized for the purpose of forming curable compositions. The curable composition containing the functionalized silicone resin can then be cured, for example, by reaction with a reactive component (e.g., a crosslinking agent) and / or by exposure to curing conditions. For example, the curable composition containing the functionalized silicone resin can be cured by heat, moisture, irradiation, etc., depending on the functionalized silicone resin used.

[0005] Conventional silicone resins are solid at room temperature or 25°C. Therefore, conventional curable compositions containing conventional silicone resins are typically solvent-based, requiring a solvent to dissolve the silicone resin. The solvent is typically discharged or volatilized before or during the end-use of the conventional curable composition. However, solvent removal adds processing steps and costs related to the end-use of conventional curable compositions utilizing such solid silicone resins. Furthermore, solvent removal generally requires high temperatures, which is unsuitable for certain end-uses of silicone resins (e.g., when placed on certain electronic devices).

[0006] UV curing of silicone compositions is often used to prepare films and coatings that are desirable to cure in the absence of heat. However, when the silicone composition contains conventional silicone resins, the silicone composition is generally solvent-based, as described above, and still requires high temperatures, if not for curing. When the silicone composition is solvent-free, the silicone composition is typically based on linear and / or partially branched organopolysiloxanes that have low viscosity and are liquid at room temperature. However, the use of linear organopolysiloxanes results in films or coatings with a lower crosslinking density compared to films formed via silicone resins, which can be undesirable as it reduces the hardness and other properties of the film or coating.

[0007] Furthermore, certain substrates on which a film or coating is formed may have complex shapes or surface features, resulting in shaded areas that are difficult to cure via UV light. Therefore, it is often desirable to use a dual curing system that can be cured via both UV light and moisture (or another curing mechanism that does not require high temperatures). However, conventional silicone resins do not contain sufficient functional groups to achieve both UV curing and moisture curing, and this also necessitates the use of linear organopolysiloxanes. [Overview of the project]

[0008] A method for preparing a film (alternatively also referred to as a coating) is disclosed. The method includes applying the composition onto a substrate to obtain an uncured layer. The method further includes irradiating the uncured layer to obtain a film. The composition includes (a) a polysiloxane resin, (b) a photoinitiator, and optionally (c) a functional diluent. (a) The polysiloxane resin includes the following siloxy units: [R3SiO 1 / 2 , [(OZ) q SiO (4-q) / 2 , [(OZ) t R MA SiO (3-t) / 2 or [(OZ) d RR MA SiO (2-d) / 2 , and at least one of them, wherein each R is independently a substituted or unsubstituted hydrocarbyl group, each R MA is independently an acryloxy functional group, each Z is independently H or an alkyl group, the subscript q is a number selected from the range of 0 to 3 in each occurrence, the subscript t is a number selected from the range of 0 to 2 in each occurrence, the subscript d is a number selected from the range of 0 to 1 in each occurrence, provided that the average concentration of the OZ group is at least 12 mole percent based on the moles of silicon atoms in the (a) polysiloxane resin.

[0009] Also disclosed are a composition for preparing a film and a film formed via the method.

Mode for Carrying Out the Invention

[0010] A method for preparing a film using a composition, and a composition for preparing a film, are disclosed and described below. The composition is curable via exposure to UV light and can also be doubly cured via moisture (i.e., condensation) in combination with irradiation. In certain embodiments, it is desirable to form a film via doubly curing of the composition to increase the crosslinking density within the film and / or to cure in areas that are difficult to reach by irradiation (e.g., shaded areas). In other embodiments, the film may be formed by irradiation alone (without moisture curing), as described below. For example, films formed by this method have excellent physical properties for use as protective and / or conformal coatings, although not limited to this particular end use. Depending on the shape of the substrate on which the film is formed, doubly curing of the film can ensure that the film is completely cured even in areas that are difficult to penetrate or reach by irradiation (e.g., due to the dimensions and / or surface characteristics of the substrate).

[0011] This composition comprises (a) a polysiloxane resin, (b) a photoinitiator, and optionally (c) a functional diluent.

[0012] (a) Polysiloxane resin has the following siloxy units: [R3SiO 1 / 2 ] and [(OZ) q SiO (4-q) / 2 ] and [(OZ) t R MA SiO (3-t) / 2 ] or [(OZ) d RR MA SiO (2-d) / 2 ] and at least one of the following. In one embodiment, (a) the polysiloxane resin is [(OZ) t R MA SiO (3-t) / 2 ] and [(OZ) d RR MA SiO (2-d) / 2] Contains both siloxy units. In other embodiments, (a) polysiloxane does not contain one of these types of siloxy units but contains the other type of siloxy unit. In (a) polysiloxane resin, each R is independently a substituted or unsubstituted hydrocarbyl group, and each R MA (a) is independently an acrylic oxy functional group, each Z is independently H or an alkyl group, the subscript q is a number selected from 0 to 3 in each occurrence, the subscript t is a number selected from 0 to 2 in each occurrence, and the subscript d is a number selected from 0 to 1 in each occurrence, provided that the average concentration of the OZ group is (a) at least 12 mole percent relative to the moles of silicon atoms in the polysiloxane resin.

[0013] As described above, each R is an independently selected hydrocarbyl group. Generally, suitable hydrocarbyl groups for R can be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can be independently monocyclic or polycyclic. Linear and branched hydrocarbyl groups can be independently saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is the aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as derivatives, variants, and combinations thereof. 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. Suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cisyloheptyl. Suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl. Suitable examples of monovalent halogenated hydrocarbon groups (i.e., halocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the alkyl groups mentioned above in which one or more hydrogen atoms are substituted with halogen atoms such as F or Cl.Specific examples of alkyl halides 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, as well as their derivatives. Examples of aryl halides include the aryl groups mentioned above, in which one or more hydrogen atoms are substituted with halogen atoms such as F or Cl. Specific examples of aryl halides include chlorobenzyl and fluorobenzyl groups.

[0014] In certain embodiments, each R is not aliphatic unsaturated (i.e., each R is neither an alkenyl nor an alkynyl group). In these or other embodiments, each R is independently an alkyl group or an aryl group. In certain embodiments, each R is independently selected from alkyl groups having 1 to 32, or 1 to 28, or 1 to 24, or 1 to 20, or 1 to 16, or 1 to 12, or 1 to 8, or 1 to 4, or 1 carbon atom.

[0015] Each R MA These are independently acrylic oxy functional groups. Typically, each R MA It independently has the following formula:

[0016] [ka] In the formula, X is a covalent bond or a divalent linking group, and R 1 R is either H or an alkyl group. 1 Suitable alkyl groups for R are disclosed above. In certain embodiments, R1 R MA H is such that it can be defined as an acrylate group. In other embodiments, R 1 R MA R is an alkyl group that can be defined as an alkyl acrylate group. In certain embodiments, R 1 R MA X is a methyl group that can be defined as a methacrylate group. In one embodiment, X is a covalent bond. In other embodiments, X is a divalent linking group. The divalent linking group is not limited and may be organic or, for example, a siloxy moiety. Typically, when X is a divalent linking group, X is a divalent hydrocarbon group. Preferred hydrocarbon groups for the divalent linking group may be substituted or unsubstituted, and may be linear, branched, and / or cyclic. However, typically, when the divalent linking group is a divalent hydrocarbon group, X is a linear unsubstituted hydrocarbon group containing 1 to 12, or 1 to 10, or 1 to 8, or 1 to 6, or 1 to 4 carbon atoms.

[0017] Each Z is independently H or alkyl group, and therefore each OZ portion is independently a hydroxyl or alkoxy group in each appearance. In certain embodiments, each OZ is independently selected from hydroxyl, methoxy, and ethoxy in each appearance. Increasing the OZ content generally increases the fluidity of the (a) polysiloxane resin (decreases its viscosity), and when the composition is water-cured, increases the rate at which the composition water-cures and forms a skin (reduces the time required). Increasing the OZ content also tends to increase glass adhesion. Therefore, higher OZ content is desirable to enhance these characteristics. In some applications, the thermal stability of the (a) polysiloxane resin may be important, and since the thermal stability of the (a) polysiloxane resin tends to decrease as the OZ content increases, an upper limit on the OZ content will be important. It may be desirable for the (a) polysiloxane resin to have a 5% weight loss temperature (by thermal gravimetric analysis (TGA)) above 150 degrees Celsius (°C). To achieve such thermal stability, the OZ content may be preferably, for example, 80 mol% or less, or 60 mol% or less, or 50 mol% or less, or 40 mol% or less, or 30 mol% or less, or 20 mol% or less. In these or other embodiments, (a) the polysiloxane resin has a partial SiOZ content of 12-80, or 15-70, or 15-60, or 15-50, or 15-40, or 15-30 percent, based on the total number of moles of Si in each molecule. Hereinafter, OZ content is relative to the moles of silicon atoms in the polysiloxane resin. Conventional silicone resins, in particular conventional silicone resins containing functional groups such as acrylicoxy functional groups, have much lower OZ content. For example, such functional groups are generally imparted to conventional silicones (e.g., via functionalized silanes) when forming conventional silicone resins. In the formation of such conventional silicone resins, condensation of OZ groups is often involved, resulting in the formation of siloxane bonds in the resulting silicone resin, which reduces the OZ content of the silicone resin.

[0018] The SiOZ content is, 29 Si nuclear magnetic resonance spectroscopy ( 29 It can be determined or measured using Si NMR. 29 Si NMR can be performed, for example, using a Varian XL-400 spectrometer. The chemical shift to the internal solvent resonance is referenced and reported for tetramethylsilane. Each siloxane unit in the resin appears at a specific position. By integrating the peak areas, it becomes possible to calculate the concentration of OZ groups relative to the silicon atoms. The peaks in the spectrum are labeled with respect to the siloxane units they correspond to, and the labels are as follows: M=R3SiO 1 / 2 D1 = R2 (OZ)SiO 1 / 2 D2 = R2SiO 2 / 2 T1 = R(OZ)2SiO 1 / 2 T2 = R(OZ)SiO 2 / 2 T3=RSiO 3 / 2 Q1 = (OZ)3SiO 1 / 2 Q2 = (OZ)2SiO 2 / 2 Q3 = (OZ)SiO 3 / 2 Q4=SiO 4 / 2 The oz content relative to silicon atoms as a mole percent can be calculated using the following formula, where each peak label in the formula corresponds to the integrated area under the peak corresponding to that label.

[0019]

number

[0020] In a particular embodiment, (a) polysiloxane is [R3SiO 1 / 2 ] and [(OZ) q SiO (4-q) / 2 ] and [(OZ) t R MA SiO(3-t) / 2 ] or [(OZ) d RR MA SiO (2-d) / 2 ] consists of at least one of the siloxy units. In other embodiments, (a) the polysiloxane is R2SiO 2 / 2 Unit (Type D unit) and / or RSiO 3 / 2 (Type T units) may further be included. Generally, as the concentration of Type D units increases, it may be desirable to include Type D units to impart linear characteristics to the (a) polysiloxane resin, which reduces the hardness of the film. In other embodiments, it may be desirable to increase the hardness of the film. In such embodiments, it may be desirable to maintain the concentration of Type D units in the (a) polysiloxane resin at an average of 10 mol% or less, preferably 5 mol% or less, more preferably 2 mol% or less, 1 mol% or less, or even 0.5 mol% or less, relative to the total moles of siloxy units. The (a) polysiloxane resin may not contain Type D siloxane units to achieve the maximum hardness of the film formed from the composition.

[0021] In a particular embodiment, (a) the polysiloxane resin has the following average formula: [W] a [X] b [Y] c [Z] d In the formula, the subscript a is greater than 0 and up to 0.5, the subscript b is between 0 and 0.5, the subscript c is greater than 0 and up to 0.5, and the subscript d is greater than 0 and up to 0.6, provided that a + b + c + d = 1. The subscripts a, b, c, and d are (a) mole fractions in W, X, Y, and Z units in the polysiloxane resin.

[0022] (a) In the above average formulas for polysiloxane resins, [W], [X], [Y], and [Z] are used instead of the more general nomenclature [M], [D], [T], and [Q]. As understood in the art, an M siloxy unit contains one siloxane bond (i.e., -O-Si-), a D siloxy unit contains two siloxane bonds, a T siloxy unit contains three siloxane bonds, and a Q siloxy unit contains four siloxane bonds.

[0023] However, for the purposes of this disclosure, [W] may be a siloxane bond or a precursor thereof, but typically represents a siloxy unit containing one -Si-O- bond which is a siloxane bond. The precursor of the siloxane bond is a -Si-OZ bond, where Z is independently selected and defined above. The silanol group and the alkoxy group hydrolyze and / or condense to provide a siloxane bond which is typically inherently present in most silicone resins. Such precursors of siloxane bonds can be minimized by thickening the silicone resin, thereby further condensing with water as a byproduct. Therefore, for the purposes of this disclosure, [W] is [R3SiO3SiO3] 1 / 2 This shows that, in the formula, each R is independently selected and defined above.

[0024] Furthermore, for the purposes of this disclosure, [X] represents a siloxy unit containing two -Si-O- bonds that may independently be a siloxane bond or a precursor thereof. Therefore, for the purposes of this disclosure, [X] represents [R2SiO 1 / 2 (OZ)] b’ [R2SiO 2 / 2 ] b’’ [RR MA SiO 2 / 2 ] b’’’ [R MA SiO 1 / 2 (OZ)] b’’’’ And in the formula, each R and R MAare independently selected, defined above, 0 ≦ b’ ≦ b, 0 ≦ b’’ ≦ b, 0 ≦ b’’’ ≦ b, 0 ≦ b’’’’ ≦ b, provided that b’ + b’’ + b’’’ + b’’’’ corresponds to b in the above average formula, and each Z is independently selected and defined above. The subscripts b’, b’’, b’’’, and b’’’’ each represent the relative molar fraction of the [X] siloxy unit indicated by each subscript with respect to the total average formula of the (a) polysiloxane resin. The [X] siloxy units represented by b’ and b’’’’ have one siloxane bond and one Si-OZ bond, and the [X] siloxy units represented by the subscripts b’’ and b’’’ have two siloxane bonds.

[0025] Furthermore, for the purposes of the present disclosure, [Y] represents a siloxy unit containing three -Si - O- bonds that can be independently a siloxane bond or its precursor. Thus, for the purposes of the present 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 and each R are independently selected and defined above, c’ is an integer from 0 to 2, and is independently selected for each Y siloxy unit indicated by the subscript c in the (a) polysiloxane resin. Thus, [Y] can represent 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 certain embodiments, the (a) polysiloxane does not contain [RSiO 3 / 2 , [RSi(OZ)1O 2 / 2 , and [RSi(OZ)2O 1 / 2 siloxy units. The siloxy unit represented by Y is RMA If it is R instead, MA The group is typically present in the X-siloxy unit described above.

[0026] Furthermore, for the purposes of this disclosure, [Z] represents a siloxy unit containing four -Si-O- bonds, which may independently be a siloxane bond or its precursor. Therefore, for the purposes of this disclosure, [Z] represents [Si(OZ)] d’ O 4-d’ / 2 [Z] is a siloxy unit represented by the following formula, where each Z is independently selected and defined above, and the subscript d' is an integer from 0 to 3 and independently selected for each siloxy unit represented by the subscript c in (a) the polysiloxane resin. (a) The polysiloxane resin may contain a siloxy unit represented by the subscript d, where d' is 0, d' is 1, d' is 2, d' is 3. A siloxy unit represented by [Z] may have 1, 2, 3, or 4 siloxane bonds, with the remainder being the Si-OZ portion. Thus, [Z] is a siloxy unit represented by the following: [SiO 4 / 2 ], [Si(OZ)O 3 / 2 ],[Si(OZ)2O 2 / 2 ], and / or [Si(OZ)3O 1 / 2 Any combination of ] can be shown.

[0027] In certain embodiments, the subscript 'a' is greater than zero and ~0.5. In certain embodiments, the subscript 'a' is 0.10 to 0.50, or 0.15 to 0.40, or 0.2 to 0.4, or 0.2 to 0.35, or 0.25 to 0.30, or 0.25 to 0.35, or 0.28 to 0.33.

[0028] In these or other embodiments, the subscript b is greater than zero and ~0.5. In certain embodiments, the subscript b is 0.01 to 0.40, or 0.02 to 0.30, or 0.03 to 0.20, or 0.04 to 0.15, or 0.05 to 0.1. In other embodiments, the subscript b is 0. The subscripts b', b'', b''', and b'''' define relative quantities of a particular siloxy unit represented by [X].

[0029] In these or other embodiments, the subscript c is greater than 0, for example, greater than 0 ~ 0.5, or 0.05 ~ 0.4, or 0.1 ~ 0.3.

[0030] In these or other embodiments, the subscript d is greater than zero and ~0.6. In certain embodiments, the subscript d is 0.35 to 0.60, or 0.40 to 0.60, or 0.40 to 0.55, or 0.45 to 0.55, or 0.45 to 0.53.

[0031] In various embodiments, the (a) polysiloxane resin has a weight-average molecular weight of 1,000 to 100,000, or 1,000 to 50,000, or 1,000 to 10,000. The molecular weight may be measured by gel permeation chromatography (GPC) against a polystyrene standard. In these or other embodiments, the (a) polysiloxane resin has a viscosity at 25°C of 10 to 500,000 cP, or 10 to 250,000 cP, or 10 to 100,000 cP. The viscosity may be measured at 25°C via a Brookfield LV DV-E viscometer equipped with a spindle appropriately selected for the viscosity of the (a) polysiloxane resin, as understood in the art. The viscosity and molecular weight of the (a) polysiloxane resin may be controlled when preparing the (a) polysiloxane resin. In other embodiments, (a) the polysiloxane resin is gum 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 flow characteristics and is considered a liquid for the purposes of this disclosure.

[0032] In certain embodiments, (a) polysiloxane resins are liquid at 25°C in the absence of any solvent. Generally, silicone resins, especially silicate resins, are solid at 25°C due to their three-dimensional network structure. Considering the difficulty of processing solid silicone resins, silicone resins are typically dissolved in a solvent and are used as silicone resin compositions containing or consisting of solid silicone resins dissolved in a solvent, such as an aliphatic or aromatic hydrocarbon solvent. Thus, silicone resin compositions are liquid at 25°C or room temperature, which allows for easier processing of the silicone resin composition. For example, silicone resin compositions can be combined with other components or compositions for various end uses in liquid form. Similarly, conventional silicone resins that are solid at 25°C in the absence of any solvent do not readily mix with liquid silicones. This means that when preparing silicone compositions, conventional silicone resins that are solid at 25°C cannot readily mix or solubilize with liquid silicones, such as liquid organopolysiloxanes, in the presence of an organic solvent. Therefore, when conventional silicone resins are used in silicone compositions, organic solvents are typically required for the purpose of forming the silicone composition and then either volatilize in composition form or volatilize during curing.

[0033] However, one drawback of silicone compositions is that the solvent is typically removed at the end of use. For example, when using a silicone composition to form a film, coating, or article, the solvent is typically removed during the formation of such a film or article. This requires additional processing steps to remove the solvent, for example, by evaporation, as well as energy and associated costs.

[0034] In contrast, the (a) polysiloxane resin of the present invention is typically liquid at 25°C in the absence of any solvent. Therefore, the fact that the (a) polysiloxane resin is liquid at 25°C is not due to the presence of any solvent, such as an organic solvent, unlike conventional silicone resins. The (a) polysiloxane resin consists of a (a) polysiloxane resin that does not contain any solvent or carrier vehicle. Furthermore, not only is the (a) polysiloxane resin liquid at 25°C in the absence of any solvent, but the (a) polysiloxane resin is also miscible with other liquid organopolysiloxanes, which makes it possible to directly incorporate the (a) polysiloxane resin into various silicone compositions in a solvent-free form, at least with respect to preparation and final composition.

[0035] "Liquid" means that (a) the polysiloxane resin is flowable at 25°C and / or has a viscosity that is measurable at 25°C in the absence of any solvent. Typically, the viscosity of (a) the polysiloxane resin is measurable at 25°C via a Brookfield LV DV-E viscometer equipped with a spindle appropriately selected for the viscosity of (a) the polysiloxane resin. The viscosity of (a) the polysiloxane resin may vary in particular 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) the polysiloxane resin may be in the form of a gum, even if the gum does not have a viscosity that is readily measurable at 25°C, since the gum still has flow characteristics.

[0036] In various embodiments, (a) the polysiloxane resin is prepared from MQ resin, where M is (R 0 SiO 3 / 2 ) refers to the siloxy unit, and Q is (SiO 4 / 2 ) refers to the siloxy unit, and in the formula, R 0'' refers to a silicon-bonded substituent. Such MQ resins are known in the art and are often in solid form (e.g., powder or flake) unless placed in a solvent. However, typically, in the nomenclature used in the art, the M-siloxy unit is a trimethylsiloxy unit, although MQ resins may contain hydrocarbyl groups other than methyl groups. However, typically, the M-siloxy unit of an MQ resin is a trimethylsiloxy unit.

[0037] MQ resin is formula M z MQ resins may contain Q units, where the subscript z represents the molar ratio of M siloxy units to Q siloxy units when the number of moles of Q siloxy units is normalized to 1. A larger value of z results in a lower crosslink density of the MQ resin. The reverse is also true, as a decrease in the value of z reduces the number of M siloxy units, and therefore more Q siloxy units can form a network without termination by M siloxy units. The fact that the MQ resin formula normalizes the Q siloxy unit content to 1 does not mean that the MQ resin contains only one Q unit. Typically, MQ resins contain multiple Q siloxy units clustered or bonded together. In certain embodiments, MQ resins may contain up to 4, or up to 3, or up to 2 weight percent of hydroxyl groups. In these or other embodiments, the MQ resin contains >1 to <12, or >8 to <11.5 mol%, of SiOH groups based on the total number of siloxy units. (a) The polysiloxane resin contains a higher molar percentage of SiOZ groups than the SiOH group content in the MQ resin.

[0038] In certain embodiments, the subscript z is <1, for example, the subscript z is 0.05 to 0.99, or 0.10 to 0.95, or 0.15 to 0.90, or 0.25 to 0.85, or 0.40 to 0.80. In these embodiments, on a molar basis, there are more Q siloxy units than M siloxy units in the MQ resin. However, in other embodiments, z may be >1, for example, >1 to 6, or >1 to 5, or >1 to 4, or >1 to 3, or >1 to 2.

[0039] In certain embodiments, to prepare (a) a polysiloxane resin from an MQ resin, the MQ resin is reacted with a silane component containing a silane compound in the presence of a catalyst. The silane compound is typically of formula R MA R x Si(OR 2 ) 3-x It has, in the formula, R MA And R are defined above, and each R 2 is an independently selected alkyl group, and the subscript x is either 0 or 1. The silane compound is a silicon-bonded acrylic oxy group (R MA (as shown by) and contains two or three silicon-bonded alkoxy groups. If the subscript x is zero, the silane compound contains three silicon-bonded alkoxy groups. If x is 1, the silane compound contains two silicon-bonded alkoxy groups. Using the silane compound, R MA (a) Acryloxic functionality is imparted to the polysiloxane resin via (a). The silicon-bonded alkoxy group can be independently selected and typically has 1 to 10, or 1 to 8, or 1 to 6, or 1 to 4, or 1 to 2, or 1 carbon atom. For example, the silicon-bonded alkoxy group may be methoxy, ethoxy, propoxy, butoxy, etc. If the subscript x is 1, the silane compound is [RR MA SiO 2 / 2 (a) It is incorporated into the polysiloxane resin as a siloxy group indicated by ]. If the subscript x is 0, the silane compound is [R MA SiO 3 / 2 (a) It is incorporated into a polysiloxane resin as a siloxy group represented by ].

[0040] Different combinations of silane compounds can be used in the silane component. For example, different types of silane compounds can be used together in the silane component. In addition, in certain embodiments, the silane component is of the formula R2Si(OR 2 The compound further comprises a second silane compound having )2, wherein R and R 2 These are each independently selected and defined above. In these embodiments, the second silane compound is [R2SiO1 / 2 (OZ)] and / or [R2SiO] 2 / 2 (a) It is incorporated into the polysiloxane resin as a siloxy group represented by ]. In these or other embodiments, the silane component is represented by formula RSi(OR 2 )3 may further comprise a third silane having 3, where R and R 2 These are each independently selected and defined above. In these embodiments, the third silane compound is [RSiO 1 / 2 (OZ)2], [RSiO 2 / 2 (OZ)], and / or [RSiO 3 / 2 (a) It is incorporated into a polysiloxane resin as a siloxy group represented by ].

[0041] (a) In the method for preparing the polysiloxane resin, a catalyst typically cleaves the siloxane bond of the MQ resin between M siloxy units and Q siloxy units, yielding an SiOZ group, where Z is defined above. The silane compound of the silane component can be hydrolyzed and condensed with the SiOZ group, incorporating it therein. The incorporation of linear siloxy units resulting from both cleaved siloxy bonds and the silane compound yields the (a) polysiloxane resin, which is liquid at 25°C in the absence of any solvent.

[0042] The relative amount of the silane component (used in comparison to the MQ resin) is a function of (a) desired subscripts b and c in the polysiloxane resin. Those skilled in the art will understand how to selectively control such content by considering the description herein, including embodiments according to embodiments for carrying out this invention.

[0043] The MQ resin and the silane compound react in the presence of a catalyst. Typically, the catalyst is an acid or a base such that the reaction between the MQ resin and the silane component is either acid-catalyzed or base-catalyzed. Typically, the reaction is base-catalyzed. Therefore, in certain embodiments, the catalyst can be selected from the group of strong acid catalysts, strong base catalysts, and combinations thereof. A strong acid catalyst may be trifluoromethanesulfonic acid, for example. The catalyst is typically a strong base catalyst. Typically, the strong base catalyst is KOH, but other base catalysts such as phosphazene base catalysts may be used.

[0044] Phosphazene catalysts generally contain at least one -(N=P<)- unit (i.e., a phosphazene unit) and are typically oligomers having up to 10 such phosphazene units, for example, having an average of 1.5 to a maximum of 5 phosphazene units. Phosphazene catalysts are, for example, halophosphazenes such as chlorophosphazene (phosphonitrile chloride), oxygen-containing halophosphazenes, ionic derivatives of phosphazenes such as phosphazenium salts, ionic derivatives of halogenated phosphonitriles in particular such as perchlorooligophosphazenium salts, or partially hydrolyzed forms thereof.

[0045] In certain embodiments, the catalyst comprises a phosphazene base catalyst. The phosphazene base catalyst may be any known in the art, but is typically the following: ((R 4 2N)3P=N) p (R 4 2N) 3-p P =NR 4 It has, in the formula, each R 4 p is independently selected from the group of hydrogen atoms, R, and combinations thereof, and p is an integer from 1 to 3. 4 If R is R 4 These are typically alkyl groups having 1 to 20, 1 to 10, or 1 to 4 carbon atoms. Any (R 4 The two R's in the 2N) portion 4The groups can bond and link to the same nitrogen (N) atom to complete a heterocycle, preferably having 5 or 6 members.

[0046] Alternatively, the phosphazene base catalyst can be a salt, and the following alternative chemical formulas [((R 4 2N)3P=N)p(R 4 2N) 3-p P=N(H)R 4 ] + [A - ]; or [((R 4 2N)3P=N) s (R 4 2N) 4-s P] + [A - ] It may have one of the following, in the formula, each R 4 is independently selected and defined above, the subscript p is defined above, the subscript s is an integer from 1 to 4, and [A] is an anion, typically selected from the group of fluorides, hydroxides, silanolates, alkoxides, carbonates, and bicarbonates. In one embodiment, the phosphazene base is aminophosphazenium hydroxide.

[0047] In certain embodiments, the MQ resin and the silane component react at a high temperature, for example, 75–125°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. The catalyst can be neutralized after the reaction using a neutralizing agent such as acetic acid. Those skilled in the art can easily determine the catalytic amount of catalyst used, which is a function of its selection and reaction conditions. The resulting (a) polysiloxane resin can be isolated or recovered from the reaction product by conventional techniques, such as stripping or other volatilization techniques.

[0048] As described above, the composition further comprises (b) a photoinitiator. (b) The photoinitiator, upon exposure to UV rays, (a) R in the polysiloxane resin MA The reaction of the groups was catalyzed. (b) The photoinitiator can be selected from any known free radical type photoinitiator that is effective in promoting the crosslinking reaction. (b) Examples of photoinitiators include diethoxyacetophenone (DEAP), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, diethoxyxanthone, chlorothioxanthone, azo-bisisobutyronitrile, N-methyldiethanolaminebenzophenone, 4,4'-bis(dimethylamino)benzophenone, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- Examples include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one, and combinations thereof.

[0049] (b) The amount of photoinitiator present in the composition is an amount effective for photocuring of the composition. In various embodiments, (b) the photoinitiator is present in the composition in an amount of about 0.01 to about 5 parts by mass, or about 0.1 to about 5 parts by mass, or about 0.1 to about 3 parts by mass, per 100 parts by mass of the total mass of the composition.

[0050] In certain embodiments, the composition further comprises (c) a functional diluent. The (c) functional diluent typically comprises a functional group selected from epoxy and acrylic groups. Examples of epoxy groups include 3-glycidoxypropyl, 4-glycidoxybutyl, or similar glycidoxyalkyl groups; 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, or similar epoxycyclohexylalkyl groups; and 4-oxyranylbutyl, 8-oxyranyloctyl, or similar oxyranylalkyl groups. An example of an acrylic group is 3-methacryloxypropyl.

[0051] In certain embodiments, (c) the functional diluent comprises a polyfunctional acrylate, the polyfunctional acrylate comprising two or more acrylicoxy functional groups.Examples of polyfunctional acrylates include (alkyl)acrylic compounds having two or more acrylic oxy or methacryloyl groups, such as trimethylolpropanedi(meth)acrylate, trimethylolpropanetri(meth)acrylate, polyoxyethylene-modified trimethylolpropanetri(meth)acrylate, polyoxypropylene-modified trimethylolpropanetri(meth)acrylate, polyoxyethylene / polyoxypropylene-modified trimethylolpropanetri(meth)acrylate, and dimethyloltricycloacrylate. Candi(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, neopentylglyceride Coll di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, o-xylylenedi(meth)acrylate, m-xylylenedi(meth)acrylate, p-xylylenedi(meth)acrylate, tris(2-hydroxyethyl)isocyanurate, tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecanedi(meth)acrylate Examples include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyoxyethylene-modified 2,2-bis(4-((meth)acrylooxy)phenyl)propane, polyoxypropylene-modified 2,2-bis(4-((meth)acrylooxy)phenyl)propane, polyoxyethylene / polyoxypropylene-modified 2,2-bis(4-((meth)acrylooxy)phenyl)propane, dipentaerythritol penta- / hexa-acrylate, and combinations thereof.

[0052] The (alkyl)acrylic compounds described above are limited to (meth)acrylate species for the sake of brevity, and those skilled in the art will readily understand that other alkyl and / or hydride versions of such compounds may be similarly available. For example, those skilled in the art will understand that the monomer “2-ethylhexyl (meth)acrylate” above exemplifies both 2-ethylhexyl (meth)acrylate and 2-ethylhexyl acrylate. Similarly, while the acrylic monomers in the above examples are generally described as propenoates (i.e., α,β-unsaturated esters), it should be understood that the term “acrylate” used in these descriptions may equally refer to the acids, salts, and / or conjugate bases of the exemplified esters. For example, those skilled in the art will understand that the monomer “methyl acrylate” above exemplifies methyl esters of acrylic acid, as well as acrylic acid, acrylate salts (e.g., sodium acrylate), etc. Furthermore, polyfunctional derivatives / variations of the above acrylic monomers may also be available. For example, the monomer "ethyl (meth)acrylate" mentioned above exemplifies functionalized derivatives such as substituted ethyl (meth)acrylate and ethyl acrylate (e.g., hydroxyethyl (meth)acrylate and hydroxyethyl acrylate, respectively).

[0053] In these or other embodiments, (c) functional diluents are 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, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, and stearyl methacrylate; vinyl acetate and vinyl propionate Vinyl esters of lower fatty acids such as tetraphosphate; vinyl esters of higher fatty acids such as vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, and vinyl stearate; aromatic vinyl monomers such as styrene, vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, and vinylpyrrolidone; amino-functional vinyl monomers such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylaminoethyl methacrylate; amide-functional vinyl monomers such as acrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, isobutoxymethoxyacrylamide, N,N-dimethylacrylamide, methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, isobutoxymethoxymethacrylamide, and N,N-dimethylmethacrylamide;Hydroxyl-functional 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 ethyl acrylate, perfluorooctyl ethyl acrylate, trifluoropropyl methacrylate, perfluorobutyl ethyl methacrylate, and perfluorooctyl ethyl methacrylate; glycidyl acrylate, 3,4-epoxycyclohexyl methyl acrylate, glycidyl methacrylate, and 3,4-epoxycyclohexyl methyl acrylate Epoxy-functional vinyl monomers such as oxycyclohexylmethyl methacrylate; ether-linked 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, polypropylene glycol monomethacrylate; alkoxysilanes containing radically polymerizable unsaturated groups, for example; ●CH2=CHCOOC3H6Si(OCH3)3, ●CH2=C(CH3)COOC3H6Si(OCH3)3, ●CH2=C(CH3)COOC3H6Si(CH3)(OCH3)2, ●CH2=C(CH3)COOC3H6Si(CH3)2OCH3, ●CH2=C(CH3)COOC2H4OC3H6Si(OCH3)3, ●CH2=C(CH3)COOC 12 H 24 Si(OCH3)3, ●CH2=CHOC3H6Si(CH3)(OC2H5)2, ●CH2=CHSi(OCH3)3, ●CH2=CHSi(OC2H5)3, and ●CH2=CHSi(C4H9)(OC4H9)2; Unsaturated group-functionalized silicone compounds such as organopolysiloxanes (branched or linear) having an acrylic or methacrylic group at one end, and polydimethylsiloxanes having a styryl group at one end; butadiene; vinyl chloride; vinylidene chloride; acrylonitrile and methacrylonitrile; dibutyl fumarate; maleic anhydride, dodecyl succinic anhydride; radically polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid, and their alkali metal salts, ammonium salts, and organic amine salts; radically 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-methacryloxypropyltrimethylammonium chloride; and methacrylate esters of alcohols containing a tertiary amine group, such as diethylamine ester of methacrylic acid, and their quaternary ammonium salts. In certain embodiments, preferred among the above are acrylate ester monomers, methacrylate ester monomers, and styrene monomers.

[0054] 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, tris(2-hydroxyethyl) isocyanurate diacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1 (c) Polyfunctional vinyl monomers can also be used as functional diluents, such as acryloyl- or methacryloyl functional monomers, which can be exemplified by acryloyl- or methacryloyl functional monomers, including ,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl methacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, diacrylates and dimethacrylates of diols obtained by adding ethylene oxide or propylene oxide to bisphenol A, and diacrylates and dimethacrylates of diols obtained by adding ethylene oxide or propylene oxide to hydrogenated bisphenol A. Polyfunctional vinyl monomers can also be used, which can also be exemplified by triethylene glycol divinyl ether and divinylbenzene.

[0055] Alternatively or additionally, (c) a functional diluent may include or have two or more acrylicoxy functional groups in an organopolysiloxane. Typically, the acrylicoxy functional groups are terminal, but may also be pendant-positioned. Organopolysiloxanes are typically linear and may have a degree of polymerization of 1 to 1,000 or 1 to 500. For example, an organopolysiloxane may be a polydimethylsiloxane with a methacrylate functional group (e.g., a 3-acrylicoxypropyl group) as a terminal group.

[0056] In these or other embodiments, (c) the functional diluent may be selected from silane compounds comprising 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloxypropyltriacetoxysilane, 2-(3,4-epoxycyclohexylethyl)trimethoxysilane, and combinations thereof.

[0057] If used, (c) the functional diluent may include a blend of different functional diluents and is typically present in the composition in an amount of more than 0 to 40 weight percent, or more than 0 to 30 weight percent, or more than 0 to 20 weight percent, or 5 to 15 weight percent, based on the total weight of the composition.

[0058] In certain embodiments, the composition further comprises (d) a condensation catalyst. The (d) condensation catalyst is used when it is desirable to double-cur the composition when forming a film, for example, by both irradiation and moisture. The moisture for the purpose of moisture curing may be ambient moisture resulting from relative humidity, i.e., it is not necessary to actively introduce moisture to bring about moisture curing. However, if desired, the moisture can be selectively controlled by increasing the relative humidity, for example, to affect the moisture curing rate.

[0059] As described above, (a) polysiloxane resin contains both acrylic oxy functional groups and a significant SiOZ content. In contrast, conventional silicone resins containing acrylic oxy functional groups typically have a much lower SiOZ content and are solid at room temperature in the absence of a solvent. However, the combination of acrylic oxy functional groups and a significant SiOZ content in (a) polysiloxane resin enables double curing via irradiation and moisture. The SiOZ content contributes to a greater crosslinking density from moisture curing than is possible with conventional silicone resins having a lower SiOZ content. These benefits are in addition to the benefits associated with (a) polysiloxane resin being liquid at room temperature.

[0060] (d) Specific examples of condensation catalysts include titanium compounds such as tetra(isopropoxy)titanium, tetra(n-butoxy)titanium, tetra(t-butoxy)titanium, di(isopropoxy)bis(ethylacetacetate)titanium, di(isopropoxy)bis(methylacetacetate)titanium, and di(isopropoxy)bis(acetylacetonate)titanium; zirconium compounds such as tetra(isopropoxy)zirconium, tetra(n-butoxy)zirconium, tetra(t-butoxy)zirconium, di(isopropoxy)bis(ethylacetacetate)zirconium, di(isopropoxy)bis(methylacetacetate)zirconium, and di(isopropoxy)bis(acetylacetonate)zirconium; and organometallic catalysts containing tin compounds such as dimethyltin dineodecanoate, dibutyltin dilaurate, dibutyltin dioctoate, and stannous octoate.

[0061] When used, the amount of (d) condensation catalyst present is an amount effective for moisture curing. In various embodiments, (d) condensation catalyst is present in an amount of about 0.01 to about 10 parts by mass, optionally about 0.05 to about 10 parts by mass, or optionally about 0.05 to about 5 parts by mass per 100 parts by mass of the total mass of the composition.

[0062] The composition may optionally further contain additive components. The additive components may be selected from the group consisting of plasticizers, surface modifiers, waxes, strengtheners, dyes, pigments, colorants, fillers, flame retardants, mold release agents, antioxidants, compatibilizers, UV stabilizers, thixotropes, anti-aging agents, lubricants, coupling agents, solvents or carrier vehicles, rheology accelerators, adhesion accelerators, thickeners, and combinations thereof.

[0063] One or more of the additives may be present in any suitable weight percent (W%) of the composition, for example, 0.1% to 15% by weight, 0.5% to 5% by weight, or 0.1% or less by weight, 1%, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% or more by weight of the composition. A person skilled in the art can easily determine a suitable amount of the additive, for example, depending on the type of additive and the desired result. Specific optional additives are described in more detail below.

[0064] A suitable carrier vehicle is considered a solvent if it can solubilize the components of the composition. Suitable carrier vehicles include silicones, both linear and cyclic organic oils, organic solvents, water (when the composition is used as an oil-in-water emulsion), and mixtures thereof. Specific examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, or xylene, and aliphatic hydrocarbons such as heptane, hexane, or octane.

[0065] In certain embodiments, the composition is substantially free of or does not contain a carrier vehicle and / or solvent. Substantially free means that the composition contains less than 5% by weight, or less than 4% by weight, or less than 3% by weight, or less than 2% by weight, or less than 1% by weight, or 0% by weight of a carrier vehicle and / or solvent based on the total weight of the composition. For the purposes of this disclosure, (c) functional diluents, which may be optionally included in the composition, are not considered carrier vehicles or solvents, even if the use of the (c) functional diluent may reduce the viscosity of the composition. In certain embodiments, the composition does not contain organic solvents.

[0066] The composition may contain one or more fillers. The fillers may be one or more reinforcing fillers, non-reinforcing fillers, or mixtures thereof. Examples of finely milled reinforcing fillers include fumed silica and settling silica with a large surface area, such as rice husk ash, and some calcium carbonate. Fumed silica may include surface-functionalized types, such as hydrophilic or hydrophobic, and is available from Cabot Corporation under the trade name CAB-O-SIL. Examples of finely milled non-reinforcing fillers include crushed quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide and carbon black, talc, and wollastonite. Other fillers that can be used alone or in combination with the above fillers include carbon nanotubes, e.g., multi-walled carbon nanotubes, aluminite, hollow glass spheres, calcium sulfate (anhydrous gypsum), gypsum, calcium sulfate, magnesium carbonate, kaolin, aluminum trihydrate, magnesium hydroxide (talc), clay, graphite, copper carbonate, e.g., malachite, nickel carbonate, e.g., zarachite, barium carbonate, e.g., basilite, and / or strontium carbonate, e.g., strontiumite. Further alternative fillers include silicates from the group consisting of aluminum oxides, olivine group, garnet group; aluminosilicates; cyclic silicates; chain silicates; and layered silicates. In certain embodiments, the composition comprises at least one filler, including hollow particles, e.g., hollow spheres. If used, fillers may be used in the composition in amounts of 0.01% to 50% by weight, 0.05% to 40% by weight, or 0.1% to 35% by weight, based on the total weight of the composition. In addition, if used, fumed silica may be used in amounts of 0.01% to 5% by weight, 0.05% to 3% by weight, 0.1% to 2.5% by weight, or 0.2% to 2.2% by weight, based on the total weight of the composition.

[0067] If used, the filler may optionally be surface-treated with a treatment agent. Treatment agents and treatment methods are well understood in the art. Surface treatment of the filler is typically carried out, for example, with fatty acid esters such as fatty acids or stearates, or with organosilanes, organosiloxanes, or organosilazanes, such as hexaalkyldisilazanes or short-chain siloxane diols. Generally, surface treatment makes the filler hydrophobic, thus facilitating handling and obtaining a homogeneous mixture with other components in the composition. 4 e Si(OR 5 ) 4-e [In the formula, R 4 R is a monovalent hydrocarbon group consisting of 6 to 20 carbon atoms, such as alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, and aralkyl groups such as benzyl and phenylethyl. 5 Silanes such as [a 1-6 carbon atom alkyl group, where the subscript e is 1, 2, or 3] can also be used as filler treatment agents.

[0068] In various embodiments, the composition further comprises an adhesion promoter. The adhesion promoter can improve the adhesion of the foam to the substrate in contact with it during curing. In certain embodiments, the adhesion promoter is selected from organosilicon compounds having at least one alkoxy group bonded to a silicone atom in the molecule. This alkoxy group is exemplified by a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group. Furthermore, the non-alkoxy groups bonded to the silicon atoms of this organosilicon compound are exemplified by, for example, substituted or unsubstituted monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and halogenated alkyl groups; epoxy group-containing monovalent organic groups such as 3-glycidoxypropyl group, 4-glycidoxybutyl group, or similar glycidoxyalkyl groups; 2-(3,4-epoxycyclohexyl)ethyl group, 3-(3,4-epoxycyclohexyl)propyl group, or similar epoxycyclohexylalkyl groups; and 4-oxyranylbutyl group, 8-oxyranyloctyl group, or similar oxyranylalkyl groups; acrylic group-containing monovalent organic groups such as 3-methacryloxypropyl group; and hydrogen atoms.

[0069] These organosilicon compounds generally have silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms. Furthermore, due to their ability to impart good adhesion to various types of substrates, these organosilicon compounds generally have at least one epoxy-containing monovalent organic group in their molecule. Examples of this type of organosilicon compound include organosilane compounds, organosiloxane oligomers, and alkyl silicates. The molecular structures of organosiloxane oligomers or alkyl silicates are exemplified by linear structures, partially branched linear structures, branched chain 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, and 3-methacryloxypropyltrimethoxysilane; siloxane compounds having at least one silicon-bonded alkenyl group or silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy group in the molecule; mixtures of silane compounds or siloxane compounds having at least one silicon-bonded alkoxy group in the molecule and siloxane compounds having at least one silicon-bonded hydroxyl group and at least one silicon-bonded alkenyl group in the molecule; and methyl polysilicate, ethyl polysilicate, and epoxy-group-containing ethyl polysilicate.

[0070] In certain embodiments, the composition essentially comprises or consists of (a) a polysiloxane resin, (b) a photoinitiator, and optionally (c) a functional diluent, optionally (d) a condensation catalyst, and optionally a filler.

[0071] This composition typically has a viscosity of greater than 0 to 50,000 cp, or 100 to 20,000 cp, or 200 to 10,000 cp, or 200 to 5,000 cp, or 200 to 1,000 cp at 25°C, even in the absence of any solvent or support. Therefore, this composition is fluid at room temperature and can form uniform coatings and films.

[0072] This composition can be used for a variety of end applications. For example, it can be used to form films with excellent physical properties, including scratch resistance. The films can be used in electronic applications (e.g., as protective or conformal coatings), in waveguides, and as protective coatings (e.g., for windows or displays, or other scratch-prone substrates). The films can also be patterned, for example, by selective curing using a photomask.

[0073] As described above, a method for preparing a film using the composition includes applying the composition onto a substrate to obtain an uncured layer. The method further includes irradiating the uncured layer to obtain a film. If the composition contains (d) a condensation catalyst, the method may further include water-curing the uncured layer and / or the film.

[0074] The composition can be applied (i.e., placed or distributed) onto a substrate in any preferred manner. Typically, the composition is applied in a wet form by wet coating techniques. 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, viiii) slot coating, ix) gravure coating, x) Meyer bar coating, or any combination of two or more of xi)i) to x). Typically, by placing the composition onto a substrate, a wet deposit or uncured layer is obtained on the substrate, which is then cured to obtain a film on the substrate.

[0075] The substrate is not limited and may be any substrate. The film may be separable from the substrate or, depending on the choice, may be physically and / or chemically bonded to the substrate. The substrate may optionally have a continuous or discontinuous shape, size, dimensions, surface roughness, and other properties.

[0076] The substrate may be an electronic article or an electronic component. In other embodiments, the substrate may include glass. Alternatively, the substrate may still include a plastic that may be thermosetting and / or thermoplastic. However, the substrate may alternatively be or include metal, ceramic, fiberglass, cellulose (e.g., paper), wood, cardboard, paperboard, silicone, or polymer materials, or a combination thereof.

[0077] Suitable substrates include paper substrates such as kraft paper, polyethylene-coated kraft paper (PEK coated paper), thermal paper, and plain paper; polymer substrates such as polyamide (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutylene; styrene resin; polyoxymethylene (POM); polycarbonate (PC); polymethylene methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); and polyphenylene ether (polyphenylene ether (PPE); polyimide (PI); polyamideimide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone; polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); polyethernitrile (PEN); phenolic resins; phenoxy resins; cellulose such as triacetylcellulose, diacetylcellulose, and cellophane; fluorinated resins such as polytetrafluoroethylene;Thermoplastic elastomers such as polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, and fluorotypes; as well as copolymers and combinations thereof.

[0078] Wet deposits or uncured layers are cured by irradiation, typically by exposure to UV rays. Useful UV sources include conventional mercury vapor lamps and LED curing lamps designed to emit UV energy across various ultraviolet wavelengths. For example, a useful radiation wavelength range is 200–400 nm. UV curing is generally performed at 40 milliwatts / cm². 2 (mW / cm 2 ) ~ approx. 30,000mW / cm 2 Within that range, for example, approximately 70 mW / cm². 2 ~About 300mW / cm 2 This is achieved within a certain range. In certain embodiments, the irradiation is carried out in an inert atmosphere, for example, under nitrogen.

[0079] If desired, the film formed by irradiating the uncured layer can be patterned. For example, in these embodiments, a photomask is typically used for selective curing of a targeted portion of the uncured layer. The photomask generally has a defined pattern for transmitting UV rays and a complementary pattern for blocking UV ray transmission. For example, the photomask includes portions that allow UV ray transmission and portions that block UV ray transmission so that the defined pattern can be transferred or copied via selective curing. The portion of the photomask that allows UV ray transmission coincides with the targeted portion of the uncured layer, and the complementary portion of the photomask that blocks UV ray transmission coincides with the non-target portion of the uncured layer. Such a method is sometimes referred to as photolithography. The targeted portion of the uncured layer is cured to obtain a cured region, and the non-target portion of the uncured layer remains uncured to obtain an uncured region.

[0080] Uncured areas of the film remaining after the use of a photomask can be etched via a wetting method, for example, using an organic solvent or a basic aqueous solution, or via a drying method (e.g., plasma or reactive ions). Typically, the uncured areas are etched or removed using solvents such as butyl acetate, alcohols, ketones, aromatic hydrocarbons, alkanes, ethers, esters, and combinations thereof. By etching or removing the uncured areas, only the cured areas are obtained, which can have 100% pattern retention.

[0081] If the composition includes (d) a condensation catalyst and the method further includes water-curing the composition (and / or a film formed from irradiation), water-curing may be achieved without any prior steps. The composition (and / or a film formed from irradiation) may be water-cured before, during, or after curing via irradiation. In one embodiment, water-curing is effective after curing via irradiation by removing the inert atmosphere and exposing the film formed from irradiation to moisture, e.g., relative humidity. When irradiation is performed in an inert atmosphere, a continuous curing step is typically used, and the inert atmosphere often does not contain ambient moisture to induce water-curing.

[0082] In certain embodiments, the film can be exposed after firing, for example, to a high temperature over a period of time. The high temperature is typically 80–140°C or 100–120°C.

[0083] A coated substrate including a film formed from this composition on a substrate may have various dimensions, including the relative thickness of the film and the substrate. The film may have a thickness that varies depending on the end application. The film may have a thickness of greater than 0 to 4,000 μm, greater than 0 to 3,000 μm, greater than 0 to 2,000 μm, greater than 0 to 1,000 μm, greater than 0 to 500 μm, or greater than 0 to 250 μm. However, other thicknesses, such as 0.1 to 200 μm, can also be conceivable. For example, the film thickness may be 0.2 to 175 μm, or 0.5 to 150 μm, or 0.75 to 100 μm, or 1 to 75 μm, or 2 to 60 μm, or 3 to 50 μm, or 4 to 40 μm. Alternatively, if the substrate is plastic, the film may have a thickness of greater than 0 to 200 μm, greater than 0 to 150 μm, or greater than 0 to 100 μm.

[0084] If desired, the film can undergo further processing depending on its end use. For example, the film can undergo oxide deposition (e.g., SiO2 deposition), resist deposition, and patterning, etching, chemical stripping, corona stripping, or plasma stripping, metal coating, or metal deposition. Such further processing techniques are generally known. Such deposition may be chemical deposition (including low-pressure chemical deposition, plasma-enhanced chemical deposition, and plasma-assisted chemical deposition), physical deposition, or other vacuum deposition techniques. Many such further processing techniques involve high temperatures, especially vacuum deposition, and given the excellent thermal stability, the film is well suited to these processes. However, depending on the film's end use, such further processing may be utilized.

[0085] The following examples are intended to illustrate the present invention and should not be considered to limit its scope. Specific components used in the examples are listed in Table 1 below, followed by the characterization and evaluation procedures also used in the examples.

[0086] [Table 1]

[0087] Nuclear Magnetic Resonance (NMR) Spectroscopy 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 29 The chemical shift of the Si-NMR spectrum is referenced to the internal solvent resonance and reported in comparison to that of tetramethylsilane.

[0088] Gel permeation chromatography (GPC) Gel permeation chromatography (GPC) analysis is performed on an Agilent 1260 Infinity II chromatograph equipped with a triple detector consisting of a differential refractometer, online differential viscometer, low-angle light scattering (LALS: detection angles of 15° and 90°), and a column (2 PL Gel Mixed C, Varian). Toluene (HPLC grade, Biosolve) is used as the mobile phase at a flow rate of 1 mL / min.

[0089] Dynamic Viscosity (DV) Dynamic viscosity (DV) was measured at 25°C using a Brookfield DV-III Ultra Programmable viscometer equipped with a CPA-52Z spindle, with a 0.5 mL sample volume.

[0090] SiOZ content The SiOZ content is, 29 This can be calculated using Si-NMR. In particular, the molar content of the following siloxy units in each polysiloxane resin can be determined. M=R'3SiO 1 / 2 D1 = R'2(OZ)SiO 1 / 2 D2 = R'2SiO 2 / 2 T1 = R'(OZ)2SiO 1 / 2 T2 = R'(OZ)SiO 2 / 2 T3=R'SiO 3 / 2 Q1 = (OZ)3SiO 1 / 2 Q2 = (OZ)2SiO 2 / 2 Q3 = (OZ)SiO 3 / 2 Q4=SiO 4 / 2 The oz content relative to silicon atoms as a mole percent can be calculated using the following formula, where each peak label in the formula corresponds to the integrated area under the peak corresponding to that label.

[0091]

number

[0092] Preparation Example 1: Polysiloxane resin (A1) 800 g of solvent (1), followed by 500 g of MQ resin, was placed in a 3 L flask equipped with a magnetic stirring rod. 340 g of silane compound (1) and 0.82 g of catalyst were placed in the flask. The contents of the flask were stirred under reflux (70°C) under nitrogen, and the progress of the reaction in the flask 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 placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 micron filter to obtain a clear, viscous liquid. Polysiloxane resin (A1) was isolated from the reaction product by removing volatile substances via a rotary evaporator. The polysiloxane resin (A1) was analyzed, and its characteristics are shown in Table 2 below.

[0093] Preparation Example 2: Polysiloxane resin (A2) 800 g of solvent (1), followed by 500 g of MQ resin, was placed in a 3 L flask equipped with a magnetic stirring rod. 340 g of silane compound (1) and 0.82 g of catalyst were placed in the flask. The contents of the flask were stirred under reflux (70°C) under nitrogen, and the progress of the reaction in the flask was monitored by GC. After it was determined (via GC) that silane compound (1) had been consumed, 18.4 g of water and 20 g of methanol were placed in the flask, and a Dean-Stark head was attached to the flask. The contents of the flask were stirred while collecting the volatile substances and replacing the volume of the collected volatile substances with solvent (1), and heated to 95°C. After reaching 95°C, the contents of the flask were cooled to 23°C, and 1.23 g of neutralizing agent was placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 micron filter to obtain a clear, viscous liquid. Polysiloxane resin (A2) was isolated from the reaction products by removing volatile substances via a rotary evaporator. The characteristics of polysiloxane resin (A2) are shown in Table 2 below.

[0094] Preparation Example 3: Polysiloxane resin (A3) 800 g of solvent (1), followed by 500 g of MQ resin, was placed in a 3 L flask equipped with a magnetic stirring rod. 340 g of silane compound (1) and 0.82 g of catalyst were placed in the flask. The contents of the flask were stirred under reflux (70°C) under nitrogen, and the progress of the reaction in the flask was monitored by GC. After it was determined (via GC) that silane compound (1) had been consumed, 18.4 g of water and 20 g of methanol were placed in the flask, and a Dean-Stark head was attached to the flask. The contents of the flask were stirred while collecting the volatile substances and replacing the volume of the collected volatile substances with solvent (1), and heated to 102°C. After reaching 102°C, the contents of the flask were cooled to 23°C, and 1.23 g of neutralizing agent was placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 micron filter to obtain a clear, viscous liquid. Polysiloxane resin (A3) was isolated from the reaction products by removing volatile substances via a rotary evaporator. The characteristics of polysiloxane resin (A3) are shown in Table 2 below.

[0095] Example 4: Polysiloxane resin (A4) 800 g of solvent (1), followed by 506 g of MQ resin, was placed in a 3 L flask equipped with a magnetic stirring rod. 340 g of silane compound (1) and 0.82 g of catalyst were placed in the flask. The contents of the flask were stirred under reflux (70°C) under nitrogen, and the progress of the reaction in the flask 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 placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 micron filter to obtain a clear, viscous liquid. Polysiloxane resin (A4) was isolated from the reaction product by removing volatile substances via a rotary evaporator. The polysiloxane resin (A4) was analyzed, and its characteristics are shown in Table 2 below.

[0096] Example 5: Polysiloxane resin (A5) 500 g of solvent (1), followed by 300 g of MQ resin, was placed in a 2 L flask equipped with a magnetic stirring rod. 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 stirred under reflux (70°C) under nitrogen, and the progress of the reaction in the flask 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 placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 micron filter to obtain a clear, viscous liquid. Polysiloxane resin (A5) was isolated from the reaction product by removing volatile substances via a rotary evaporator. The polysiloxane resin (A5) was analyzed, and its characteristics are shown in Table 2 below.

[0097] Example 6: Polysiloxane resin (A6) 500 g of solvent (1), followed by 300 g of MQ resin, was placed in a 2 L flask equipped with a magnetic stirring rod. 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 stirred under reflux (70°C) under nitrogen, and the progress of the reaction in the flask was monitored by GC. After it was determined (via GC) that silane compounds 1 and 2 had been consumed, 11 g of water and 20 g of methanol were placed in the flask, and a Dean-Stark head was attached to the flask. The contents of the flask were stirred while collecting the volatile substances and replacing the volume of the collected volatile substances with solvent (1), and heated to 105°C. 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 micron filter to obtain a clear, viscous liquid. Polysiloxane resin (A6) was isolated from the reaction products by removing volatile substances via a rotary evaporator. The characteristics of polysiloxane resin (A6) are shown in Table 2 below.

[0098] Example 7: Polysiloxane resin (A7) 200 g of solvent (1), followed by 100 g of MQ resin, was placed in a 1 L flask equipped with a magnetic stirring rod. 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 stirred under reflux (70°C) under nitrogen, and the progress of the reaction in the flask 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 placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 micron filter to obtain a clear, viscous liquid. Polysiloxane resin (A7) was isolated from the reaction product by removing volatile substances via a rotary evaporator. The polysiloxane resin (A7) was analyzed, and its characteristics are shown in Table 2 below.

[0099] Example 8: Polysiloxane resin (A8) 200 g of solvent (1), followed by 100 g of MQ resin, was placed in a 1 L flask equipped with a magnetic stirring rod. 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 stirred under reflux (70°C) under nitrogen, and the progress of the reaction in the flask was monitored by GC. After it was determined (via GC) that silane compounds 1 and 3 had been consumed, 3.7 g of water and 10 g of methanol were placed in the flask, and a Dean-Stark head was attached to the flask. The contents of the flask were stirred while collecting the volatile substances and replacing the volume of the collected volatile substances with solvent (1), and heated to 105°C. 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 micron filter to obtain a clear, viscous liquid. Polysiloxane resin (A8) was isolated from the reaction products by removing volatile substances via a rotary evaporator. The characteristics of polysiloxane resin (A8) are shown in Table 2 below.

[0100] In Preparation Examples 1-8, the polysiloxane resin prepared above was used 29 Analysis was performed via Si-NMR, GPC, and DV. The results are shown in Table 2 below.

[0101] [Table 2]

[0102] Examples 1-24 and Comparative Examples 1-2 Compositions were prepared using polysiloxane resins (A1) to (A8). The components and relative amounts used in each of Examples 1 to 24 and Comparative Examples 1 to 2 are shown in Table 3 below. In Table 3, the polysiloxane resin, photoinitiator, and functional diluent, and the specific species used, are identified (based on Table 1) along with their relative amounts. For example, for the photoinitiator, "(1) 2.0" indicates 2 grams of photoinitiator (1). In Table 3, CE indicates a comparative example. Each composition was prepared by placing the components in an amber-colored dental mixing cup and mixing them.

[0103] [Table 3]

[0104] Films were prepared using the compositions of Examples 1-24 and Comparative Examples 1-2. In particular, each composition was coated onto a glass substrate using a drawdown bar to obtain a 250 micrometer thick coating on the glass substrate. Each coating was then exposed to UV light (0.5 joule broadband) at 23°C under nitrogen using a Fusion Systems Corporation instrument model 31983-E to obtain a cured film. Each cured film was then analyzed and considered "failed" if it was liquid or sticky to the touch. A cured film was considered "acceptable" if it was non-liquid and non-sticky to the touch (as reported in Table 4 below).

[0105] Some of the films formed using the compositions of Examples 1-24 and Comparative Examples 1-2 were double-cured via water curing following the UV curing step described above. For coatings that were double-cured, the cured films formed after exposure to UV rays were placed (on a glass substrate) in an environment of 23°C and 50% relative humidity. For 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 skin curing time. The skin curing time was recorded based on the time it took for the sample to form a skin. Cured films with a skin curing time of less than 4 hours were considered "acceptable," and those that did not form a skin or had a skin curing time exceeding 4 hours were considered "unacceptable" (as reported in Table 4 below). The skin curing time was measured in relation to water curing. Therefore, for films that were UV-cured only and not double-cured, the skin curing time was measured separately based on water curing in the absence of any UV curing. The last column of Table 4, which indicates whether the film has been UV-cured or double-cured, relates to pencil hardness and adhesion value (described below), but not to skin curing time.

[0106] The cured films were analyzed for pencil hardness according to ASTM D3363-05. For cured films formed solely by exposure to UV light, the pencil hardness was determined after UV curing. For double-cured films, the pencil hardness was measured after UV curing, followed by 6 days of moisture curing. The results of the pencil hardness tests are shown in Table 4 below.

[0107] The cured film was analyzed for adhesion to glass according to ASTM D3359 using the Gardco PA-2000 adhesion test kit. For cured films formed only by UV exposure, adhesion to glass was determined after UV curing. For double-cured cured films, adhesion to glass was measured after 6 days of moisture curing. The results of the pencil hardness test are shown in Table 4 below. The adhesion analysis to glass includes cross-hatching of the cured film. A rating of "1" means insufficient adhesion, with more than 50% of the cured film being removed. A rating of "2" means adequate adhesion, with 5-50% of the cured film being removed. A rating of "3" means good adhesion, with less than 5% of the cured film being removed.

[0108] [Table 4] * Skin curing time based on moisture curing

[0109] Example 25 A patterned film was prepared in Example 25. First, a composition was prepared by combining 8.8 grams of polysiloxane resin (A1), 1.0 gram of functional diluent (1), 0.2 grams of photoinitiator (1), 0.3 grams of silane compound (1), and 9.7 grams of propylene glycol methyl ether acetate. The composition was mixed and passed through a 0.2 micron filter to remove the solid and obtain a solution. The solution was spin-coated onto a 4-inch silicon wafer using a Karl Suss CT62 spin coater to obtain 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 gas purging, and then placed in a mask aligner with a photomask having 5-100 micron line / space. The coating on the silicon wafer was purged under nitrogen at 1.0 J / cm². 2When a silicon wafer was exposed to a UV broadband source (200-380 nm) at a specified dose, followed by exposure to 110°C for 60 seconds on a hot plate and then firing, a partially cured film was formed on the silicon wafer. The partially cured film contained both cured and uncured portions. Next, the partially cured film on the silicon wafer was immersed in butyl acetate at room temperature for 60 seconds to remove the uncured portions and form a patterned film corresponding to the negative of the photomask. When the patterned film was examined under a microscope, it showed a line / space pattern with a resolution of 5 μm and 100% pattern retention.

[0110] Example 26 A patterned film was prepared in Example 26. First, a composition was prepared by combining 8.8 grams of polysiloxane resin (A5), 1.0 gram of functional diluent (2), 0.2 grams of photoinitiator (1), 0.3 grams of silane compound (1), and 9.7 grams of propylene glycol methyl ether acetate. The composition was mixed and passed through a 0.2 micron filter to remove the solid and obtain a solution. The solution was spin-coated onto a 4-inch silicon wafer using a Karl Suss CT62 spin coater to obtain 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 gas purging, and then placed in a mask aligner with a photomask having 5-100 micron line / space. The coating on the silicon wafer was purged under nitrogen at 1.0 J / cm². 2 When a silicon wafer was exposed to a UV broadband source (200-380 nm) at a specified dose, followed by exposure to 110°C for 60 seconds on a hot plate and then firing, a partially cured film was formed on the silicon wafer. The partially cured film contained both cured and uncured portions. Next, the partially cured film on the silicon wafer was immersed in butyl acetate at room temperature for 60 seconds to remove the uncured portions and form a patterned film corresponding to the negative of the photomask. When the patterned film was examined under a microscope, it showed a line / space pattern with a resolution of 5 μm and 100% pattern retention.

[0111] Definitions and Use of Terms The abbreviations used in this specification have the definitions shown in Table 5 below.

[0112] [Table 5]

[0113] It should be understood that the attached claims are intended to express "modes for carrying out the invention" and are not limited to the specific compounds, compositions, or methods described herein, and may vary among the specific embodiments that fall within the scope of the attached claims.

Claims

1. A method for preparing a film, wherein the method is The composition is applied to a substrate to obtain an uncured layer, Irradiating the aforementioned uncured layer, This includes exposing the uncured layer to moisture to prepare the film, The composition is (a) A polysiloxane resin comprising the following siloxy units: [R ３ SiO １／２ , [(OZ) ｑ SiO （４－ｑ）／２ , [(OZ) ｔ R ＭＡ SiO （３－ｔ）／２ or [(OZ) ｄ RR ＭＡ SiO （２－ｄ）／２ , wherein each R is independently a substituted or unsubstituted hydrocarbyl group, each R ＭＡ is independently an acryloxy functional group, each Z is independently H or an alkyl group, the subscript q is a number selected from the range of 0 to 3 in each occurrence, the subscript t is a number selected from the range of 0 to 2 in each occurrence, and the subscript d is a number selected from the range of 0 to 1 in each occurrence, provided that the average concentration of the OZ group is at least 12 mol percent based on the moles of silicon atoms in the (a) polysiloxane resin, (a) polysiloxane resin, and (b) Photoinitiator and optionally (c) Functional diluents and (d) A method comprising a condensation catalyst.

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

3. (i) The method according to claim 1 or 2, wherein the (a) polysiloxane resin is liquid at 25°C in the absence of any solvent, or (ii) the composition contains no 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 the (c) functional diluent is epoxy and / or acrylicoxy functional.

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

6. Each R ＭＡ However, independently, the following formula: 【Chemistry 1】 The formula has a covalent bond or a divalent linking group, and R １ The method according to claim 1 or 2, wherein is H or an alkyl group.

7. The method according to claim 1 or 2, further comprising placing a photomask on the composition before and / or during curing such that the film includes a patterned film having a cured region and an uncured region.

8. The method according to claim 7, further comprising removing the uncured region from the patterned film using a solvent.

9. SiO ４／２ The method further includes preparing the (a) polysiloxane resin (a) by reacting a silicone resin containing siloxy units with a silane component containing a silane compound in the presence of a catalyst to obtain the (a) polysiloxane resin, The silane compound, formula R ＭＡ R ２ ｘ Si ( OR ２ ) ３－ｘ It has, in the formula, each R ＭＡ Each R is independently an acrylic oxy functional group, ２ The method according to claim 1 or 2, wherein is an independently selected alkyl group having 1 to 4 carbon atoms, and the subscript x is 0 or 1.

10. A composition, (a) Polysiloxane resin, wherein the following siloxy units: [R ３ SiO １／２］ and [(OZ) ｑ SiO （４－ｑ）／２ ] and [(OZ) ｔ R ＭＡ SiO （３－ｔ）／２ ] or [(OZ) ｄ RR ＭＡ SiO （２－ｄ）／２ The formula includes at least one of the following, where each R is independently a substituted or unsubstituted hydrocarbyl group, and each R ＭＡ (a) a polysiloxane resin, wherein each Z is independently an acrylic oxy functional group, each Z is independently H or an alkyl group, the subscript q is a number selected from the range of 0 to 3 in each occurrence, the subscript t is a number selected from the range of 0 to 2 in each occurrence, and the subscript d is a number selected from the range of 0 to 1 in each occurrence, provided that the average concentration of OZ groups is at least 12 mole percent relative to the moles of silicon atoms in the (a) polysiloxane resin, (b) Photoinitiator and optionally (c) Functional diluents and (d) A composition comprising a condensation catalyst.

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