CURABLE SILICONE COMPOSITIONS AND THEIR APPLICATIONS AND USES

Abstract

A curable composition comprising (A) an organopolysiloxane containing curable functional groups; and (B) a silicone-free organic material containing reactive functional groups. The curable composition exhibits high refractive index and optical clarity. The curable composition can be used to prepare cured materials that exhibit high refractive index, optical clarity, crack resistance, and low water vapor permeability. [Selection diagram] None

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Application No. 15 / 627,482, filed June 20, 2017, the disclosure of which is incorporated herein by reference in its entirety.

[0002] The present invention relates to a curable silicone composition. In particular, the present invention relates to a curable silicone composition comprising an organopolysiloxane and a silicone-free organic material. The curable silicone composition can be used to form a cured material that can exhibit one or more of a high refractive index, good water vapor permeability, high heat resistance, crack resistance, and optical clarity. The curable composition can be used in a variety of applications, including as a sealant, encapsulant, barrier coating layer, and the like, and can find application in a variety of environments, including electronic devices. [Background technology]

[0003] Many of the next generation flexible printed electronic displays, including organic light-emitting diodes (OLEDs), organic photovoltaic displays (OPVs), and organic thin-film transistors (OTFTs), are highly sensitive to atmospheric water vapor and oxygen, limiting the lifetime of the display devices and their widespread commercialization.

[0004] The current encapsulation technology commonly available for field or moisture sensitive organic electronic devices is a glass lid with a getter material secured to the substrate by an epoxy adhesive. The getter material, such as calcium oxide or barium oxide, is placed in the package to react with any by-products of the resin curing process or residual water that has entered the package or diffuses through the epoxy seal over time. Glass is widely used as an encapsulant or barrier layer due to its low permeability to water vapor and oxygen, but the main drawback of glass encapsulation technology is that the resulting devices are non-flexible and rigid, failing to satisfy applications calling for flexible devices.

[0005] Several attempts have been made to develop flexible barrier films. These include multilayer systems (often 10 or more layers) with alternating inorganic and organic layers. Such systems are described, for example, in WO00 / 36665 A1, WO 01 / 81649 A1, WO 2004 / 089620 A2, WO 03 / 094256 A2, and WO 2008 / 057045 A1. Although multilayer thin film techniques provide good barrier properties and serve the purpose of encapsulation in electronic devices, the complex nature and high cost of thin film preparations make them not feasible for large area and large scale manufacturing processes. It is therefore desirable to provide substrates with improved barrier properties that can protect display devices from premature degradation and extend their lifespan. Summary of the Invention

[0006] The following presents a summary of the disclosure to provide a basic understanding of some aspects. This summary is not intended to identify key or critical elements or to define limitations of the embodiments or claims. Moreover, this summary may provide a simplified overview of some aspects that may be described in more detail in other parts of the disclosure.

[0007] According to various aspects and embodiments, the present technology provides a curable silicone composition comprising an organopolysiloxane and a silicone-free organic material. The organopolysiloxane comprises an organic functional group in the polysiloxane backbone. It has been found that the cured material formed from the composition comprising such organopolysiloxane exhibits a relatively high refractive index, good optical transparency (e.g., low yellowing), flexibility, heat resistance, crack resistance, and / or moisture permeability.

[0008] In various aspects, the present invention provides curable compositions suitable for thin film flexible encapsulation techniques that not only reduce the overall complexity but also provide high quality barrier films that are scalable and easily processable for manufacturing large area display devices.

[0009] The present invention, in its aspects and embodiments, provides a low moisture permeable siloxane composition, which provides a cured material with a high refractive index and / or improved barrier properties suitable for use in organic electroluminescent display devices and can extend their life span. In one aspect, the present invention provides a curable composition of a bicyclic modified silicone-containing compound, where the bicyclic compound can be present at a terminal position, as a pendant group, and / or in the backbone of a silicone polymer. Methods for producing the bicyclic modified silicone-containing compound and methods for producing a cured material from the composition are disclosed.

[0010] In one aspect, the present invention provides a method for producing (A) an organopolysiloxane having the formula: [ka] Here, R 1 is a divalent organic group selected from a C1-C20 divalent hydrocarbon, a C4-C20 branched divalent hydrocarbon, or a C4-C30 cyclic-containing hydrocarbon group; R 2 is a curable functional group independently selected from vinyl, vinyl-containing groups, unsaturated hydrocarbons, unsaturated cyclic hydrocarbons, acrylates, methacrylates, hydroxys, alkoxys, and epoxy; R 3 -R 14 are independently selected from hydrogen, a C1-C10 monovalent hydrocarbon radical, a C6-C20 monovalent aromatic radical, and a C4 to C30 monovalent saturated or unsaturated cycloalkyl radical, a siloxy radical containing 1-20 silicon atoms; x and z are independently 1-30; y and w are independently 0-30; and n is 1-30; and (B) Silicone-free organic materials containing reactive functional groups The present invention provides a curable silicone composition comprising:

[0011] In one embodiment of the curable silicone composition, R 1are cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1,1-diethenylcyclohexane; 1,3-diethenylcyclohexane; bicyclo[2.2.1]-2,5-diethenylheptane; 1,4-di-2-prop-1-ylcyclohexane; 1,3-diisopropenylbenzene; spiro[5.5]-3,8-diethenylundecane; 1,3-diethenyl adamantane; vinylnorbornene; 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane; pinane, bornane, norpinane, norbornane, spiro[2.2]pentane, spiro[2.3]hexane, spiro[2.4]heptane, spiro[2.5]octane, spiro[3.3]heptane, spiro[3.4]octane, spiro[3.5]nonane, spiro[4.4]nonane, spiro[4.5]decane, spiro[5.5]undecane, bicyclo[1.1.0]butane, bicyclo[2.1.0]pentane, bicyclo[2.2.0]hexane, bicyclo[3.1.0]hexane, bicyclo[3.2.0]heptane, bicyclo[3.3.0]octane, bicyclo[4.1.0]heptane, bicyclo[4.2.0]octane, bicyclo[4.3.0]nonane, bicyclo[4.4.0]decane cane, bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.1.1]heptane, bicyclo[3.2.1]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, bicyclo[3.3.2]decane, bicyclo[3.3.3]undecane, adamantyl, tricyclo[5.2.1.0 2,6 ]Decane Tricyclo[4.3.1.1 2,5 ]undecane ring, and a divalent group containing a C4-C30 cyclic-containing hydrocarbon group selected from the group consisting of

[0012] In one embodiment of the curable silicone composition of the above embodiment, R 2 is selected from a C1-C20 hydrocarbon radical containing a vinyl functionality, a monovalent C4-C20 branched hydrocarbon radical containing a vinyl functionality, or a monovalent C4-C30 cyclic hydrocarbon radical containing a vinyl functionality.

[0013] In one embodiment of the curable silicone composition of the above embodiment, R 2 Formula XR 16 -, X is a curable functional group selected from a vinyl group (CH2=CH2-), an unsaturated cyclic group, and an unsaturated polycyclic group, R 16 is a bond or a monovalent hydrocarbon. In one embodiment, X is cyclopentene, cyclohexene, cyclooctene, pinene, bornene, norpinene, norbornene, spiro[2.2]pentene, spiro[2.3]hexene, spiro[2.4]heptene, spiro[2.5]octene, spiro[3.3]heptene, spiro[3.4]octene, spiro[3.5]nonene, spiro[4.4]nonene, spiro[4.5]decene, spiro[5.5]undecene, bicyclo[1.1.0]butene, bicyclo[2.1.0]pentene, bicyclo[2.2.0]hexene, bicyclo[3.1.0]hexene, bicyclo[3.2.0]hexene, butene, bicyclo[3.3.0]octene, bicyclo[4.1.0]heptene, bicyclo[4.2.0]octene, bicyclo[4.3.0]nonene, bicyclo[4.4.0]decene, bicyclo[1.1.1]pentene, bicyclo[2.1.1]hexene, bicyclo[2.2.1]heptene, bicyclo[2.2.2]octene, bicyclo[3.1.1]heptene, bicyclo[3.2.1]octene, bicyclo[3.2.2]nonene, bicyclo[3.3.1]nonene, bicyclo[3.3.2]decene, bicyclo[3.3.3]undecene, adamantene, tricyclo[5.2.1.0 2,6 ]Decen, Tricyclo[4.3.1.1 2,5 ] undecene ring, limonene, camphene, limonene oxide, vinylcyclohexyl epoxide, dicyclopentadiene, 5-ethylidene-2-norbornene, 2-vinyladamantane, 2-methyleneadamantane, dicyclopentadiene, or (-)-beta-camigrene, 4-vinylcyclohexyl.

[0014] In one embodiment of the curable silicone composition of the previous embodiment, the organic material (B) is selected from vinyl-terminated polyisobutene. In one embodiment of the curable silicone composition of the previous embodiment, the polyisobutene has a number average molecular weight of 200 to about 40,000. In one embodiment of the curable silicone composition of the previous embodiment, the polyisobutene has a number average molecular weight of 900 to about 3,000.

[0015] In one embodiment of the curable silicone composition of the foregoing embodiments, the curable silicone composition comprises (C) a crosslinker selected from a compound containing at least one -SiH group, at least one -SH group, or a combination of two or more thereof, (D) a reaction accelerator selected from a photoinitiator, a thermal initiator, a metal-containing catalyst, or a combination of two or more thereof, (E) an inhibitor, and / or (F) one or more additives.

[0016] In one embodiment of the curable silicone composition of the foregoing embodiment, the crosslinker (C) is selected from a silicone-containing compound containing at least one -SiH group, at least one -SH group, or a combination of two or more thereof. In one embodiment, the silicone-containing compound is selected from a cyclic silicone, a linear silicone, a branched silicone, or a combination of two or more thereof.

[0017] In one embodiment of the curable silicone composition of the previous embodiments, the reaction accelerator is selected from a metal-containing catalyst.

[0018] In one embodiment of the curable silicone composition of the foregoing embodiments, the inhibitor is selected from an ethylenic compound, an acetylenic compound, or a combination thereof.

[0019] In one embodiment of the curable silicone composition of the foregoing embodiments, the additive is selected from an antioxidant, a heat stabilizer, an adhesion promoter, a filler, or a combination of two or more thereof.

[0020] In one embodiment of the curable silicone composition of the previous embodiments, the composition has a refractive index of from 1.45 to 1.51.

[0021] In one embodiment of the curable silicone composition of the foregoing embodiments, the composition has a transparency of at least 95%, and even greater than 98%.

[0022] In one embodiment of the curable silicone composition of the above embodiment, the composition is -1 From 10g / m 2 The MVTR, WVTR, and O permeability are shown.

[0023] In one aspect, the present invention provides a cured article formed from the curable composition of the above-described embodiments.

[0024] In one aspect, the present invention provides a cured article formed from a curable silicone composition, the curable silicone composition comprising: (A) an organopolysiloxane having the following formula: [ka] Here, R 1 is a divalent organic group selected from a C1-C20 divalent hydrocarbon, a C4-C20 branched divalent hydrocarbon, or a C4-C30 cyclic-containing hydrocarbon group; R 2 is a curable functional group independently selected from vinyl, vinyl-containing groups, unsaturated hydrocarbons, unsaturated cyclic hydrocarbons, acrylates, methacrylates, hydroxys, alkoxys, and epoxy; R 3 -R 14 are independently selected from hydrogen, a C1-C10 monovalent hydrocarbon radical, a C6-C20 monovalent aromatic radical, and a C4 to C30 monovalent saturated or unsaturated cycloalkyl radical; x and z are independently 1 to 30; y and w are independently 0-30, and n is 1 to 30, (B) comprises an organic material that is silicone-free and contains reactive functional groups. Optionally, the composition may include other components, such as (C) a crosslinker selected from a compound containing at least one -SiH group, at least one -SH group, or a combination of two or more thereof; (D) a reaction accelerator selected from a photoinitiator, a thermal initiator, a metal-containing catalyst, or a combination of two or more thereof; (E) an inhibitor; and / or (F) one or more additives.

[0025] In one embodiment, R 1 are cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1,1-diethenylcyclohexane; 1,3-diethenylcyclohexane; bicyclo[2.2.1]-2,5-diethenylheptane; 1,4-di-2-prop-1-ylcyclohexane; 1,3-diisopropenylbenzene; spiro[5.5]-3,8-diethenylundecane; 1,3-diethenyl adamantane; vinylnorbornene; 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane; pinane, bornane, norpinane, norbornane, spiro[2.2]pentane, spiro[2.3]hexane, spiro[2.4]heptane, spiro[2.5]octane, spiro[3.3]heptane, spiro[3.4]octane, spiro[3.5]nonane, spiro[4.4]nonane, spiro[4.5]decane, spiro[5.5]undecane, bicyclo[1.1.0]butane, bicyclo[2.1.0]pentane, bicyclo[2.2.0]hexane, bicyclo[3.1.0]hexane, bicyclo[3.2.0]heptane, bicyclo[3.3.0]octane, bicyclo[4.1.0]heptane, bicyclo[4.2.0]octane, bicyclo[4.3.0]nonane, bicyclo[4.4.0]decane cane, bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.1.1]heptane, bicyclo[3.2.1]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, bicyclo[3.3.2]decane, bicyclo[3.3.3]undecane, adamantyl, tricyclo[5.2.1.0 2,6 ]Decane Tricyclo[4.3.1.1 2,5]undecane ring.

[0026] In one embodiment of the cured article of the previous embodiment, R 2 The functional group is selected from a C1-C20 hydrocarbon radical containing a vinyl functionality, a monovalent C4-C20 branched hydrocarbon radical containing a vinyl functionality, or a monovalent C4 to C30 cyclic hydrocarbon radical containing a vinyl functionality.

[0027] In one embodiment of the cured article of the previous embodiment, R 2 The base is the formula XR 16 where X is a curable functional group and R 16 is a bond or a monovalent hydrocarbon radical. In one embodiment, R 16 may be a C1-C20 alkylene group; a C1-C10 alkylene group; or even a C1-C6 alkylene group, and X may be selected from a vinyl group (CH2=CH2-), an unsaturated cyclic group, or an unsaturated polycyclic group.

[0028] In one embodiment, X is cyclopentene, cyclohexene, cyclooctene, pinene, bornene, norpinene, norbornene, spiro[2.2]pentene, spiro[2.3]hexene, spiro[2.4]heptene, spiro[2.5]octene, spiro[3.3]heptene, spiro[3.4]octene, spiro[3.5]nonene, spiro[4.4]nonene, spiro[4.5]decene, spiro[5.5]undecene, bicyclo[1.1.0]butene, bicyclo[2.1.0]pentene, bicyclo[2.2.0]hexene, bicyclo[3.1.0]hexene, bicyclo[3.2.0]hexene, butene, bicyclo[3.3.0]octene, bicyclo[4.1.0]heptene, bicyclo[4.2.0]octene, bicyclo[4.3.0]nonene, bicyclo[4.4.0]decene, bicyclo[1.1.1]pentene, bicyclo[2.1.1]hexene, bicyclo[2.2.1]heptene, bicyclo[2.2.2]octene, bicyclo[3.1.1]heptene, bicyclo[3.2.1]octene, bicyclo[3.2.2]nonene, bicyclo[3.3.1]nonene, bicyclo[3.3.2]decene, bicyclo[3.3.3]undecene, adamantene, tricyclo[5.2.1.0 2,6 ]Decen, Tricyclo[4.3.1.1 2,5 ]undecene ring, limonene, camphene, limonene oxide, vinylcyclohexyl epoxide, dicyclopentadiene, 5-ethylidene-2-norbornene, 2-vinyladamantane, 2-methyleneadamantane, dicyclopentadiene, (-)-beta-camigrene, 4-vinylcyclohexyl.

[0029] In one embodiment of the cured article of the foregoing embodiments, the crosslinker (B) is selected from a silicone-containing compound containing at least one -SiH group, at least one -SH group, or a combination of two or more thereof.

[0030] In one embodiment, the silicone-containing compound is selected from cyclic silicones, linear silicones, branched silicones, or a combination of two or more thereof.

[0031] In one embodiment of the cured article of the foregoing embodiments, the accelerant is selected from a metal-containing catalyst.

[0032] In one embodiment of the cured article of the foregoing embodiments, the inhibitor is selected from an ethylenic compound or an acetylenic compound or a combination thereof.

[0033] In one embodiment of the cured article of the foregoing embodiments, the additives are selected from antioxidants, heat stabilizers, adhesion promoters, fillers, or combinations thereof.

[0034] In one embodiment of the cured article of the foregoing embodiments, the article has a refractive index of 1.45 to 1.51.

[0035] In one embodiment of the cured article of the foregoing embodiments, the article has a transparency of 95% or greater, or even greater than 98%.

[0036] In one embodiment of the cured article of the previous embodiments, the article is 10 -1 From 10g / m 2 In one embodiment, the cured article formed from the composition has an MVTR, WVTR, and permeability of 3 g / m 2 It has a water vapor permeability of less than 10 ...

[0037] In one embodiment of the cured article of the foregoing embodiments, the article is selected from an LED encapsulant, a light guide, an optical lens, an optical bond, an optical adhesive, an optical film or sheet, a laminated film of sheets in combination with an electronic component or semiconductor device.

[0038] In yet another aspect, the present invention provides a personal care composition comprising the curable silicone composition of any of the preceding embodiments, hi one embodiment, the personal care composition is selected from a cosmetic formulation, a sunscreen, a shampoo, a conditioner, a lotion, or a cream. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0039] Reference will now be made to exemplary embodiments, examples of which are illustrated in the accompanying drawings. It will be understood that other embodiments may be utilized and that structural and functional changes may be made. Additionally, features of the various embodiments may be combined or modified. As such, the following description is presented for illustrative purposes only and is in no way intended to limit the various alternatives and modifications that may be made to the illustrated embodiments. In this disclosure, numerous specific details are set forth to provide a thorough understanding of the subject disclosure. It should be understood that aspects of the present disclosure may be implemented in other embodiments, including but not limited to all aspects set forth herein.

[0040] As used herein, the words "example" and "exemplary" mean an example or illustration. The words "example" or "exemplary" do not indicate a primary or preferred aspect or embodiment. The word "or" is intended to be inclusive rather than exclusive, unless the context suggests otherwise. For example, the phrase "A uses B or C" includes inclusive permutations (e.g., A uses B; A uses C; or A uses both B and C). As a separate matter, the articles "a" and "an" are generally intended to mean "one or more," unless the context suggests otherwise.

[0041] The present technology provides a curable composition comprising: (A) an organopolysiloxane comprising a curable functional group; and (B) a silicone-free organic material. The composition may also include other components, such as, for example, (C) a crosslinker comprising a silyl hydride group or a thiol group; (D) a reaction accelerator; (E) an inhibitor; and / or (F) other additives.

[0042] The organopolysiloxane (A) comprises a siloxane polymer having organic functional groups between silicon atoms within a portion of the main chain. The organopolysiloxane (A) comprises a compound of formula (I): [ka] Here, R 1 is a divalent organic group selected from a C1-C20 hydrocarbon, a C4-C20 branched hydrocarbon, or a C4-C30 cyclic-containing hydrocarbon group; R 2 is a curable functional group independently selected from vinyl, vinyl-containing groups, unsaturated hydrocarbons, unsaturated cyclic hydrocarbons, acrylates, methacrylates, hydroxys, alkoxys, and epoxy; R 3 -R 14 are independently selected from hydrogen, a C1-C10 monovalent hydrocarbon radical, a C6-C20 monovalent aromatic radical, and a C4 to C30 monovalent saturated or unsaturated cycloalkyl radical, a siloxy radical containing 1-20 silicon atoms; x and z are independently 1-30; y and w are independently 0-30; and n is 1 to 30.

[0043] R 1 may be selected from a divalent C1-C20 hydrocarbon or a divalent C4-C20 branched divalent hydrocarbon group. A divalent hydrocarbon group is a group formed by removing two hydrogen atoms from an alkane (two hydrogen atoms from the same carbon or one hydrogen atom from two different carbon atoms). Examples of suitable divalent hydrocarbon groups include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, isopropylene, isobutylene, and the like. In an embodiment, R 1 is selected from C1-C6 straight or branched chain alkylene.

[0044] R 1can also be selected from divalent cyclic hydrocarbon groups. As used herein, a "cyclic" or "cyclic-containing" hydrocarbon group refers to a group derived from a cyclic-containing alkane by removing two hydrogen atoms, where (i) both hydrogen atoms may be removed from the same ring carbon, (ii) one hydrogen atom is removed from one ring carbon and one hydrogen atom is removed from another ring carbon, (iii) one hydrogen is removed from a ring carbon and one hydrogen is removed from a hydrocarbon group attached to a chain, (iv) both hydrogen atoms are removed from the same carbon of a hydrocarbon group attached to a cyclic group, or (v) one hydrogen is removed from a first hydrocarbon group attached to a cyclic group and one hydrogen is removed from a second hydrocarbon group attached to a cyclic group.

[0045] The cyclic group in the cyclic-containing hydrocarbon may be a monocyclic hydrocarbon group or a polycyclic hydrocarbon group.Suitable examples of monocyclic hydrocarbon groups include, but are not limited to, cycloalkyl groups having 3 to 12 carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, or cycloalkenyl groups having 3 to 12 carbon atoms, such as cyclohexenyl.In an embodiment, the monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms.Cyclopentyl and cyclohexyl groups are particularly suitable.

[0046] Polycyclic hydrocarbon groups include ring assembly hydrocarbon groups and bridged ring hydrocarbon groups. Examples of ring assembly hydrocarbon groups include bicyclohexyl groups, perhydronaphthalene groups, etc. Examples of bridged ring hydrocarbon rings include, for example, tetracyclo[4.4.0.1 2,5 .1 7,10]Bridged ring hydrocarbon rings include, but are not limited to, bicyclic, tricyclic, and tetracyclic hydrocarbon rings, such as dodecane and perhydro-1,4-methano-5,8-methanonaphthalene rings.Furthermore, bridged ring hydrocarbon rings include fused ring hydrocarbon rings, such as those resulting from the fusion of multiple 5- to 8-membered cycloalkane rings, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings.

[0047] R 1 It may be part of a group or R 1 Examples of suitable polycyclic hydrocarbon groups from 4 to 30 which may provide the group include pinane, bornane, norpinane, norbornane, spiro[2.2]pentane, spiro[2.3]hexane, spiro[2.4]heptane, spiro[2.5]octane, spiro[3.3]heptane, spiro[3.4]octane, spiro[3.5]nonane, spiro[4.4]nonane, spiro[4.5]decane, spiro[5.5]undecane, bicyclo[1.1.0]butane, bicyclo[2.1.0]pentane, bicyclo[2.2.0]hexane, bicyclo[3.1.0]hexane, bicyclo[3.2.0]heptane , bicyclo[3.3.0]octane, bicyclo[4.1.0]heptane, bicyclo[4.2.0]octane, bicyclo[4.3.0]nonane, bicyclo[4.4.0]decane, bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.1.1]heptane, bicyclo[3.2.1]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, bicyclo[3.3.2]decane, bicyclo[3.3.3]undecane, adamantyl, tricyclo[5.2.1.0 2,6 ]Decane Tricyclo[4.3.1.1 2,5 ]undecane ring, but is not limited to these.

[0048] In embodiments, the cyclic R 1 The group has the formula R 15 -AR 15where R 15 R is a bond or a C1-C10 monovalent hydrocarbon radical and A is a cyclic or polycyclic hydrocarbon group. The cyclic or polycyclic group A can be any cyclic or polycyclic group described above. 15 It is understood that the groups may be attached to the same ring carbon atom or to different carbon atoms on the ring.

[0049] R 1 Examples of suitable groups include, but are not limited to, the following: [ka]

[0050] R 1 The divalent organic radicals or "alkylene" type radicals of R are described with respect to removal of hydrogen. 1 is converted to the desired R 1 It will be understood by those skilled in the art of forming silicone-containing materials that the siloxanes may be derived from and incorporated into the siloxane backbone by reaction of a diene (conjugated or non-conjugated) compound containing groups with an appropriate siloxane.

[0051] R 2 R is a group containing a curable functional group selected from vinyl, acrylate, methacrylate, hydroxyl, alkoxy, alkenyloxy, or epoxy. 2 R may be selected from a monovalent C1-C20 hydrocarbon radical containing a curable functional group, a monovalent C4-C20 branched hydrocarbon radical containing a curable functional group, or a monovalent C4-C30 cyclic hydrocarbon radical containing a curable functional group. 2 The group, in embodiments, has the formula XR 16 -, where X is a curable functional group, and R 16 is a bond or a monovalent hydrocarbon group. In embodiments, R 16can be a C1-C20 alkylene group; a C1-C10 alkylene group; and a C1-C6 alkylene group. X can be selected from vinyl groups (CH2=CH2-), unsaturated cyclic groups, unsaturated polycyclic groups, and the like. In embodiments, X is selected from the group consisting of cyclopentene, cyclohexene, cyclooctene, pinene, bornene, norpinene, norbornene, spiro[2.2]pentene, spiro[2.3]hexene, spiro[2.4]heptene, spiro[2.5]octene, spiro[3.3]heptene, spiro[3.4]octene, spiro[3.5]nonene, spiro[4.4]nonene, spiro[4.5]decene, spiro[5.5]undecene, bicyclo[1.1.0]butene, bicyclo[2.1.0]pentene, bicyclo[2.2.0]hexene, bicyclo[3.1.0]hexene, bicyclo[3.2.0]hexene, butene, bicyclo[3.3.0]octene, bicyclo[4.1.0]heptene, bicyclo[4.2.0]octene, bicyclo[4.3.0]nonene, bicyclo[4.4.0]decene, bicyclo[1.1.1]pentene, bicyclo[2.1.1]hexene, bicyclo[2.2.1]heptene, bicyclo[2.2.2]octene, bicyclo[3.1.1]heptene, bicyclo[3.2.1]octene, bicyclo[3.2.2]nonene, bicyclo[3.3.1]nonene, bicyclo[3.3.2]decene, bicyclo[3.3.3]undecene, adamantene, tricyclo[5.2.1.0 2,6 ]Decen, Tricyclo[4.3.1.1 2,5 ]undecene ring, limonene, camphene, limonene oxide, vinylcyclohexyl epoxide, dicyclopentadiene, 5-ethylidene-2-norbornene, 2-vinyladamantane, 2-methyleneadamantane, dicyclopentadiene, (-)-beta-camigrene, 4-vinylcyclohexyl, and the like.

[0052] Appropriate R 2 Or examples of X groups include, but are not limited to, the following: [ka]

[0053] In embodiments, the polymer may include an aromatic group bonded to one of the silicon atoms, e.g., R 3 -R 14 In an embodiment, R in the polymer 5 and R 11 The group comprises an aromatic group. In an embodiment, the aromatic group is a phenyl group. Without being bound to a particular theory, the presence of an aryl group may be desirable to limit the mobility of the silicon atom.

[0054] In embodiments, the organopolysiloxane (A) comprises a polycyclic group and an aromatic group. The polycyclic group is a siloxane chain (e.g., R 1 ) in the middle and terminal positions (i.e., R 2 In embodiments, R 5 and R 11 The group comprises an aromatic group. In one embodiment, the organopolysiloxane (A) is a compound of the formula: [ka] In another embodiment, the organopolysiloxane (A) is a compound of the formula: [ka]

[0055] The silicone-free organic material (B) is selected from organic monomers or oligomers having reactive functional groups. As used herein, reactive functional groups may also be referred to as curable functional groups. The reactive functional groups may be selected from, but are not limited to, ethylenically unsaturated monomers (e.g., allyl, vinyl, etc.), ethylenically unsaturated aromatic compounds, ethylenically unsaturated acids, ethylenically unsaturated anhydrides, acrylates, methacrylates, acrylamides, or combinations of two or more thereof. Non-limiting examples of vinyl ether monomers include, for example, methyl, ethyl, propyl, isobutyl, 2-ethylhexyl, cyclohexyl, 4-hydroxybutyl, decyl, dodecyl, octadecyl, 2-(diethylamino)ethyl, 2-(di-n-butylamino)ethyl and methyl diglycol vinyl ethers, the corresponding allyl alkyl ethers, and combinations thereof. Non-limiting examples of ethylenically unsaturated acid and anhydride monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and maleic acid and their anhydrides, monovinyl adipate, and combinations thereof. Non-limiting examples of olefin monomers include, for example, ethylene, propylene, butene, isobutylene, pentene, cyclopentene, hexane, cyclohexene, octane, 1-3 butadiene, chloroprene, cyclobutadiene, isoprene, and combinations thereof. Non-limiting examples of ethylenically unsaturated aromatic compounds include, for example, styrene, alkylstyrene, and chlorostyrene.

[0056] In one embodiment, the organic material (B) is selected from functionalized isobutylene compounds. The polyisobutene has a number average molecular weight M of at least 200. n In embodiments, the polyisobutene may have a number average molecular weight M ranging from 200 to 40,000, 500 to 15,000, 700 to 7,000, 900 to 3,000, and even 900 to 1,100. n As used herein, the term "polyisobutene" also includes oligomeric isobutene, such as dimer, trimer, tetramer, pentamer, hexamer, and heptamer isobutene.

[0057] The reactivity of polyisobutene increases with increasing concentration of reactive functional groups. In an embodiment, the polyisobutene comprises at least 50 mol% reactive functional groups; at least 60 mol% reactive functional groups; or even at least 80 mol% reactive functional groups. In one embodiment, the polyisobutene comprises at least 50 mol% terminal double bonds based on the total number of polyisobutene polymers; at least 60 mol% terminal double bonds, or even at least 80 mol% terminal double bonds based on the total number of polyisobutene polymers. The terminal double bonds can be either vinyl double bonds [CH=C(CH3)2] (β-olefins) or vinylidene double bonds [CH-C(=CH2)-CH3] (α-olefins). A substantially homopolymeric polyisobutene radical can have a uniform polymer backbone. In an embodiment, the polyisobutene system is formed in at least 85 wt%, at least 90 wt%, or even at least 95 wt% of the repeating unit [CH2C(CH3)2-] of isobutene units.

[0058] The polyisobutene may, in embodiments, have a polydispersity index (PDI) of from 1.05 to 10, from 1.05 to 3.0, or even from 1.05 to 2.0. Polydispersity refers to the ratio of the weight average molecular weight M w and number average molecular weight M n Ratio to (PDI=M w / M n ) is shown.

[0059] Polyisobutenes suitable for use in the composition include all polymers obtained by cationic polymerization and, in copolymerized form, contain at least 60% by weight of isobutene, at least 80% by weight, at least 90% by weight, or even at least 95% by weight of isobutene. In addition, the polyisobutenes may contain, in copolymerized form, further butene isomers, such as 1- or 2-butene, and different olefinically unsaturated monomers copolymerizable with isobutene under cationic polymerization conditions.

[0060] Suitable isobutene feedstocks for the preparation of polyisobutene include both isobutene itself and isobutene C4 hydrocarbon streams, such as C4 raffinate, C4 fraction from isobutene dehydrogenation, C4 fraction from steam cracker, FCC cracker (FCC: fluid catalytic cracking), provided that they are substantially free of 1,3-butadiene present therein. Particularly suitable C4 hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm, of butadiene. When C4 fractions are used as starting materials, hydrocarbons other than isobutene play the role of inert solvent.

[0061] Useful monomers copolymerizable with isobutene include vinyl aromatics such as styrene and α-methylstyrene, C1-C4-alkylstyrenes such as 2-, 3- and 4-methylstyrene, and isoolefins having from 5 to 10 carbon atoms such as 4-tert-butylstyrene, 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1.

[0062] Examples of polyisobutenes suitable for the composition include, but are not limited to, Glissopal® brands, such as Glissopal 550, Glissopal 1000, and Glissopal 2300, manufactured by BASF Aktiengesellschaft, and Oppanol® brands, such as Oppanol B10, B12, and B15, manufactured by BASF Aktiengesellschaft.

[0063] In another embodiment, the organic material (B) may be selected from an acrylate monomer, an acrylate oligomer, or a combination thereof. As used herein, an acrylate monomer or an acrylate oligomer refers to a monomer or an oligomer that contains one or more acryloyl groups, one or more methacryloyl groups, or one or more acryloyl groups and one or more methacryloyl groups, respectively. In an embodiment, the acrylate monomer or oligomer may be an epoxy acrylate, a urethane acrylate, an aminated acrylate, or the like. It will be understood that the monomers and / or oligomers may contain one or more acryloyl or methacryloyl groups such that they may be monoacrylates, diacrylates, triacrylates, or the like.

[0064] In one embodiment, the organic material (B) can include an acrylate monomer. Examples of suitable acrylate monomers include 2-butoxyethyl acrylate, 2-butoxyethyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-ethyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-hydroxyethyl acrylate, 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, benzyl acrylate, cyclohexyl acrylate, di(ethylene glycol) ethyl ether acrylate, di(ethylene glycol) ethyl ether methacrylate, di(ethylene glycol) methyl ether methacrylate, dicyclofentanyl acrylate, epoxy acrylate, ethylene glycol methyl ether acrylate, ethylene glycol phenyl ether acrylate, hydroxypropyl acrylate, isobornyl acrylate, methyl adamantyl acrylate, neopentyl glycol benzoate acrylate, 2-hydroxymethyl methacrylate, adamantyl methacrylate, methyl ... The acrylates include, but are not limited to, acrylate, alkyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, epoxycyclohexylmethyl methacrylate, ethylene glycol phenyl ether methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, methyl adamantyl methacrylate, methyl methacrylate, methyl glycidyl methacrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, alkyl acrylates, 2-hydroxyacrylates, trimethoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3-fluoroethyl acrylate, 4-fluoropropyl acrylate, and triethylsiloxylethyl acrylate, or a combination of two or more thereof.

[0065] In one embodiment, the organic material (B) comprises a multifunctional (meth)acrylate monomer. The multifunctional (meth)acrylate monomer can be saturated or unsaturated and can include aliphatic, cycloaliphatic, aromatic, heterocyclic, and / or epoxy functional groups. In some embodiments, saturated long chain alkyl (meth)acrylates, cycloaliphatic (meth)acrylates, (meth)acrylate / epoxy monomers, or combinations thereof can be utilized as monomers. The multifunctional (meth)acrylate monomers can be unsubstituted or substituted with various groups, such as hydroxy or alkoxy groups.

[0066] Exemplary long chain alkyl (meth)acrylates include, but are not limited to, octyl (meth)acrylate, stearyl (meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and hydrogenated polybutadiene di(meth)acrylate resins. Exemplary cycloaliphatic (meth)acrylates include, but are not limited to, isobornyl (meth)acrylate, tetramethylpiperidiyl methacrylate, pentamethylpiperidiyl methacrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and (meth)acrylated epoxies.

[0067] Examples of commercially available acrylate monomers include, but are not limited to, acrylate monomers under the trade names EM210®, EM211®, EM221®, EM2230®, EM231®, EM235®, EM265®, EM70®, EM215®, EM218® or EM2108® manufactured by Eternal company.

[0068] In another embodiment, the organic material (B) can include an acrylate oligomer. Examples of suitable acrylate oligomers include, but are not limited to, those having a molecular weight of about 1,000 to 100,000. In an embodiment, the acrylate oligomer can be selected from polyester (meth)acrylates, urethane (meth)acrylates, alkoxylated (meth)acrylate oligomers, epoxy (meth)acrylates, aminated (meth)acrylates, (meth)acrylate (meth)acrylics, or combinations of two or more thereof.

[0069] Examples of suitable acrylate oligomers include, but are not limited to, acrylates, such as 2-hydroxy-3-phenoxypropyl acrylate; methacrylates; urethane acrylates, such as aliphatic urethane acrylates, aliphatic urethane diacrylates, aliphatic urethane hexaacrylates, aromatic urethane hexaacrylates, or acrylate-terminated urethanes; epoxy acrylates, such as bisphenol A epoxy diacrylate or novolac epoxy acrylate; or combinations of two or more thereof.

[0070] Examples of suitable commercially available acrylate oligomers include, but are not limited to, SR454®, SR494®, SR9020®, SR9021®, or SR9041® from Sartomer company; 6101-100®, 611A-85®, 6112-100®, 6113®, 6114®, 6123®, 6131®, 6144-100®, 6145-100®, 6150-100®, 6160B-70®, 621A-80®, or 621-100® from Eternal company; and Ebecryl 600®, Ebecryl 83 ... Included are acrylate oligomers with the tradenames 3605® or Ebecryl 6700®.

[0071] Examples of suitable polyester (meth)acrylates include, but are not limited to, acrylated epoxidized soybean oil compounds such as EBECRYL® 860 (Cytec), fatty acid-containing polyester (meth)acrylates such as EBECRYL® 870, EBECRYL® 657, EBECRYL® 450 (Cytec), and polyester (meth)acrylates such as EBECRYL® 800, EBECRYL® 884, EBECRYL® 810 and EBECRYL® 830 (Cytec).

[0072] Examples of suitable epoxy (meth)acrylates include, but are not limited to, di(meth)acrylate of diglycidyl ether of bisphenol A (BADGED(M)A) and modifications thereof (see, for example, EBECRYL® 3700 or EBECRYL® 600, EBECRYL® 3701, EBECRYL® 3703, EBECRYL® 3708 and EBECRYL® 3639 from Cytec). Examples of suitable urethane (meth)acrylates include, but are not limited to, EBECRYL® 284, EBECRYL® 264, EBECRYL® 210, EBECRYL® 230, EBECRYL® 1290 (Cytec). Examples of suitable aminated (meth)acrylates include, but are not limited to, EBECRYL® 80, EBECRYL® 81, EBECRYL® 83, EBECRYL® 7100, P115, and others. Examples of suitable (meth)acrylic (co)polymers that can be used include, but are not limited to, EBECRYL® 745 and / or EBECRYL® 1200. Examples of suitable inert polyesters include, but are not limited to, EBECRYL® 525, and optionally its chlorinated variants (e.g., EBECRYL® 436 and others).

[0073] The crosslinker (C) comprises a functional group that reacts with the curable functional group of the organopolysiloxane (a). In an embodiment, the crosslinker (b) comprises a Si-H group, an SH group, a vinyl group, a vinyl-containing group, an unsaturated hydrocarbon, an unsaturated cyclic hydrocarbon, an acrylate, a methacrylate, a hydroxy, an alkoxy, an epoxy, or a combination of two or more thereof. In an embodiment, the crosslinker is selected from a linear silicone, a branched silicone, or a cyclic silicone material that comprises a Si-H or SH group. It will be understood that a combination of different crosslinker compounds can be used if desired.

[0074] In an embodiment, the crosslinker (C) is selected from silyl hydrides. The silyl hydrides are not particularly limited. In an embodiment, the silyl hydrides are represented by the formula R 17 g SiH 4-g , (R 17 O) g SiH 4-3 , HSiR 17 g (OR 17 ) 3-g , R 17 3Si(CH2) f (SiR 17 2O) k SiR 17 2H, (R 17 O)3Si(CH2) f (SiR 17 2O) k SiR 17 2H, Q u T v T p H D t D H s M H r M e , R 17 3Si(CH2) h SiOSiR 17 2(OSiR 17 2) j OSiR 17 2H, or a combination of two or more thereof. 17Each occurrence of is independently C1-C18 alkyl, C1-C18 substituted alkyl, where R 17 optionally contains at least one heteroatom, each occurrence of g independently has a value from 0 to 3, f has a value from 1 to 8, k has a value from 0 to 3000, p, u, v, r, and e each independently have a value from 0 to 20, t and s are from 0 to 3000, with the proviso that p+s+r is equal to 1 to 1000, and the valences of all elements of the silyl hydride are satisfied. 18 3SiO 1 / 2 D represents a monofunctional group of the formula R 18 2SiO 2 / 2 T represents a bifunctional group of the formula R 18 SiO 3 / 2 and Q represents a trifunctional group of the formula SiO 4 / 2 represents a tetrafunctional group, and M H HR 18 2SiO 1 / 2 represents T H HSiO 3 / 2 and D H is R 18 HSiO 2 / 2 R 18 Each occurrence of is independently C1-C18 alkyl, C1-C18 substituted alkyl, where R 18 optionally contains at least one heteroatom; h is 1 to 8 and j is 0 to 10.

[0075] Some non-limiting examples of silyl hydrides include methylhydrogensiloxydimethylsiloxane copolymers, such as those from Gelest, such as HMS 501HPM-502, HMS-992, HMS-064, polyhydrosilsesquioxanes, and other hydride-containing copolymers or homopolymers of dimethylsiloxanes or phenyl-containing siloxanes. Other suitable silyl hydrides include those present in SYLGARD 184, a commercial two-part silicone from DowComing of Midland, Mich, which is provided without the thermal hydrosilylation catalyst typically included in commercial versions. [ka]

[0076] The following structure shows an example of an organohydrogenpolysiloxane with phenyl functionality (HDP-111 - hydride terminated polyphenyl(dimethylhydrosiloxy)siloxane available from Gelest Inc. of Tullytown, Pa.). [ka]

[0077] Other examples of silyl hydride agents include Q resins, which may also be referred to as HQ-type resins or hydride-modified silica Q resins. Examples of these compounds include, but are not limited to, those commercially available under the trade names MQH-9™ (Clariant LSM, Inc.), which is a hydride-modified silica Q resin characterized by a molecular weight of 900 g / mole and an activity of 9.5 equivalents / kg; HQM 105™ (Gelest, Inc.), which is a hydride-modified silica Q resin characterized by a molecular weight of 500 g / mole and an activity of 8-9 equivalents / kg; and HQM 107™ (Gelest, Inc.), which is a hydride-modified silica Q resin characterized by a molecular weight of 900 g / mole and an activity of 8-9 equivalents / kg.

[0078] Examples of suitable mercapto-functional siloxanes include, but are not limited to, products such as KF-2001 and KF-2004 manufactured by Shin-Etsu Chemical Co., Ltd., SMS-022, SMS-042 and SMS-992 manufactured by Gelest Inc., PS848, PS849, PS849.5, PS850, PS850.5 and PS927 manufactured by United Chemical Corp, and B 7610 manufactured by Momentive Performance Materials Inc.

[0079] The crosslinker (C) may also be selected from compounds of the formula: [ka] Here, R 19 is a divalent organic group selected from a C1-C20 divalent hydrocarbon, a C4-C20 branched divalent hydrocarbon, or a C4-C30 cyclic-containing divalent hydrocarbon group; R 20 is hydrogen, acrylate, methacrylate, thiol, or R 2 is a functional group selected from; R 21 -R 32 is hydrogen, a C1-C10 monovalent hydrocarbon radical, C 6 -C 20 independently selected from a monovalent aromatic group, and a C4 to C30 monovalent cycloalkyl group; a and d are independently 1 to 30; b and c are independently 0-30; and m is 1 to 30.

[0080] R 19 is the above R 1 The R 21 -R 32 is the above R 3 -R 14 However, for the sake of brevity, the details of those groups will not be repeated.

[0081] The composition includes an accelerant (D) that effects curing of the organopolysiloxane (A), the organic material (B), and the crosslinker (C). The accelerant (D) may be, for example, a photoinitiator, a thermal initiator, a metal catalyst, or a combination of two or more thereof.

[0082] In embodiments, the reaction promoter comprises a catalyst, such as a hydrosilylation catalyst. Useful catalysts include compounds or molecules capable of catalyzing a hydrosilylation reaction between a reactive SiH-containing moiety or substituent and a carbon-carbon bond, such as a carbon-carbon double bond. Also, in one or more embodiments, these catalysts may be soluble in the reaction medium. Classes of catalysts include transition metal compounds, including compounds containing Group VIII metals. Exemplary Group VIII metals include palladium, rhodium, germanium, and platinum. Exemplary catalyst compounds include chloroplatinic acid, elemental platinum, chloroplatinic acid hexahydrate, complexes of chloroplatinic acid with sym-divinyltetramethyldisiloxane, dichloro-bis(triphenylphosphine)platinum(II), cis-dichloro-bis(acetonitrile)platinum(II), dicarbonyldichloroplatinum(II), platinum chloride, and platinum oxide, zero-valent platinum metal complexes such as Karstedt's catalyst, [Cp * Ru(MeCN)3]PF6, [PtCl2(cyclooctadiene)], solid platinum supported on a support (alumina, silica, carbon black, etc.), platinum-vinylsiloxane complexes (e.g., Pt n (ViMe2SiOSiMe2Vi) n and Pt[(MeViSiO)4] m )), platinum-phosphine complexes (e.g., Pt(PPh3)4 and Pt(PBU3)4), and platinum phosphite complexes (e.g., Pt[P(Oph)3]4 and Pt[P(Obu)3]4), where Me represents methyl, Bu represents butyl, "Vi" represents vinyl, Ph represents phenyl, and n and m represent integers. Others include RhCl(PPh3)3, RhCl3, Rh / Al2O3, RuCl3, IrCl3, FeCl3, AlCl3, PdCl2·2H2O, NiCl2, TiCl4, etc.

[0083] In embodiments, photoinitiators may be used as reaction promoters to promote the curing of siloxanes. Photoinitiators can be selected depending on the particular purpose or intended application. Examples of suitable photoinitiators include, but are not limited to, benzophenone, phosphine oxide, nitroso compounds, acrylic halides, hydrazones, mercapto compounds, pyrylium compounds, triacrylimidazole, benzimidazole, chloroalkyl triazine, benzoin ether, benzil ketal, thioxanthone, camphorquinone, acylphosphine, and acetophenone derivatives.

[0084] In one embodiment, the photoinitiator is selected from acylphosphines. The acylphosphine can be a mono- or bis-acylphosphine. Examples of suitable acylphosphine oxides include those described in U.S. Pat. No. 6,803,392, which is incorporated herein by reference. Specific examples of suitable acylphosphine photoinitiators include, but are not limited to, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (DAROCUR® TPO), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (ESACURE® TPO, LAMBERTIChemical Specialties, Gallate, Italy), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (FIRSTCURE® HMPP, available from Albemarle Corporation, Baton Rouge, La.), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (LUCIRIN® TPO, available from BASF (Ludwigshafen, available from Ciba Specialty Chemicals, Tarrytown, NY), diphenyl(2,4,6-trimethylbenzoyl)phosphineate (LUCIRIN® TPO-L), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (IRGACURE® 819, available from Ciba Specialty Chemicals, Tarrytown, NY), and bis(2,6-di-methoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (as IRGACURE® 1700, IRGACURE® 1800 and IRGACURE® 1850 in mixtures with α-hydroxyketones from Ciba Spezialitaetenchemie).

[0085] Examples of α-hydroxyketone photoinitiators can include 1-hydroxy-cyclohexyl phenyl ketone (IRGACURE® 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (DAROCUR® 1173), and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (IRGACURE® 2959), all available from Ciba Specialty Chemicals (Tarrytown, NY).

[0086] Examples of α-aminoketone photoinitiators can include 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (IRGACURE® 369) and 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone (IRGACURE® 907), both available from Ciba Specialty Chemicals (Tarrytown, NY).

[0087] The curable composition may optionally include a polymerization inhibitor (E). The polymerization inhibitor is not particularly limited and may be selected according to the particular purpose or intended use. Component (E) of the inhibitor (inhibitor) of platinum group metal catalysts is well known in the art of organosilicon. Examples of suitable inhibitors include, but are not limited to, ethylenically unsaturated amides, aromatically unsaturated amides, acetylenic compounds, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon monoesters of unsaturated acids, conjugated or isolated ene-ynes, hydroperoxides, ketones, sulfoxides, amines, phosphines, phosphites, nitrites, diaziridines, and the like. Particularly suitable inhibitors for the composition are alkynyl alcohols and maleates. Examples of suitable polymerization inhibitors include, but are not limited to, diallyl maleate, hydroquinone, p-methoxyphenol, t-butyl catechol, phenothiazine, and the like.

[0088] The amount of component (E) used in the composition is not critical and may be any amount that retards the platinum-catalyzed hydrosilylation reaction described above at room temperature without interfering with said reaction at moderately elevated temperatures, i.e., 25 to 125° C. above room temperature. A specific amount of inhibitor to obtain a specific bath life at room temperature cannot be suggested, since the desired amount of a specific inhibitor used will depend on the concentration and type of platinum metal-containing catalyst, and the nature and amount of components a and b. Component (E) may range from 0 to about 10% by weight, from about 0.001 to 2% by weight, or even from about 0.12 to about 1% by weight. Here, as elsewhere in the specification and claims, numerical values ​​may be combined to form new alternative ranges. In one embodiment, the composition may be free of inhibitor component (E).

[0089] The curable composition may also include other additives (F), which may include, but are not limited to, adhesion promoters, antioxidants, fillers, pigments, dyes, filler treatments, plasticizers, spacers, extenders, biocides, stabilizers, flame retardants, surface modifiers, anti-aging additives, rheology additives, corrosion inhibitors, surfactants, or combinations thereof.

[0090] A variety of organofunctional silane and siloxane adhesion promoters to inorganic substrates are useful in the composition. Suitable silanes include, but are not limited to, aminosilanes, epoxysilanes, isocyanurate silanes, mercaptosilanes, imidosilanes, anhydride silanes, carboxylate-functionalized siloxanes, and the like. Combinations of various types of adhesion promoters may also be used. Such components would normally prevent cure by metal-catalyzed hydrosilylation. Suitable adhesion promoters include, but are not limited to, various amino silane materials available from Momentive Performance Materials, such as Silquest® A-1120 silane, Silquest A-1110 silane, Silquest A-2120 silane, and Silquest A-1170 silane; epoxy silanes, such as Silquest A-187 silane; isocyanurate silanes, such as Silquest A-597 silane; and mercapto silanes, such as Silquest A-189 silane, Silquest A-1891 silane, Silquest A-599 silane.

[0091] The curable compositions may also include an antioxidant compound. Examples of suitable classes of antioxidant compounds include, but are not limited to, hindered amine and / or hindered phenol compounds.

[0092] Examples of hindered amine antioxidant compounds include, but are not limited to, the hindered amine antioxidants (N,N',N'',N'''-tetrakis-(4,6-bis(butyl-(N-methyl)-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine-N-(2,2,6,6- Polycondensation products of tetramethyl-4-piperidyl)butylamine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], polymers of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis(2,2,6,6-tetramethyl-1(octyl)decanedioate] 1,2,2,6,6-pentamethyl-4-piperidyl) ester, reaction products of 1,1-dimethylethyl hydroperoxide and octane](70%)-polypropylene (30%), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, etc.

[0093] In one embodiment, the antioxidant compound is a hindered phenol compound. The hindered phenol can be selected according to a specific purpose or application. Examples of suitable hindered phenols include, but are not limited to, monophenols such as 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, and 2,6-t-butyl-4-ethylphenol, bisphenols such as 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butylphenol);and polymeric phenols such as 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis(4'-hydroxy-3-t-butylphenyl)butyric acid glycol ester, and tocopherol (vitamin E), pentaerythritol-tetrakis[3-(3,5-di-t tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide], benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6-(1-methylethyl) ethylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3'',5,5',5''-hexane-tert-butyl-4-a,a',a''-(mesitylene-2,4,6-tolyl)tri-p-cresol, calcium diethyl bis[[[3,5-bis-(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate], 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl) hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, reaction products of N-phenylbenzenamine with 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, etc.;

[0094] IRGANOX 1330 is a sterically hindered phenolic antioxidant ("3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4,6-triyl)tri-p-cresol") commercially available from BASF. Irganox 1010 is a sterically hindered phenolic antioxidant commercially available from BASF ("pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)"), or 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene is commercially available as ETHANOX™ 330 (Albemarle Corporation), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (Irganox 3114), tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate is commercially available as Irganox 3114.

[0095] The curable composition may optionally contain a light stabilizer. The light stabilizer is not particularly limited and may be selected according to a particular application or intended use. Examples of materials suitable for the light stabilizer include, but are not limited to, 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(21-1-benzotriazol-2-yl)-5-tert-butyl- 4-Hydroxyphenyl)propionate / Polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-6-(linear and branched dodecyl)-4-methylphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL, MARK LA-57, LA-62, LA-67, LA-63, SANDOL LS-765, LS-292, LS-2626, LS-1114, LS-744, and the like.

[0096] The curable composition may include organopolysiloxane (A) in an amount of about 5 to about 98% by weight; about 10 to about 90% by weight; or about 20 to about 80% by weight. The curable composition may include organic material (B) in an amount of about 2 to about 95% by weight; about 10 to about 90% by weight; or about 20 to about 80% by weight. Crosslinker (C) may be present in an amount of about 2 to about 25% by weight; about 6 to about 20% by weight; or about 6 to about 12% by weight. Reaction accelerator (C) may be present in an amount of about 0.0001 to about 0.2% by weight; about 0.0002 to about 0.05% by weight; or about 0.0005 to about 0.02% by weight. The inhibitor (D) may be present in an amount of about 0.0001 to about 1% by weight; about 0.0002 to about 0.6% by weight; or about 0.0005 to about 0.3% by weight. The adhesion promoter may be present in an amount of about 0.1 to about 10% by weight; about 0.3 to about 5% by weight; or about 0.5 to about 3% by weight.

[0097] The curable composition has various properties that can make the composition and the cured materials formed therefrom useful in various applications. For example, the curable composition can have a refractive index greater than about 1.40, 1.45, 1.5, 1.55, or 1.60. In embodiments, the curable composition has a refractive index of about 1.40 to about 1.6, or about 1.45 to about 1.55.

[0098] The curable compositions may also exhibit excellent optical clarity, in embodiments, the curable compositions have a clarity of about 95% or greater, about 96% or greater, about 97% or greater, about 98% or greater, or even about 99% or greater from 400 nm to about 800 nm.

[0099] In addition, the viscosity of the composition may be controlled or adjusted over a wide range of viscosities as desired to allow for control in processing of the composition as may be required for the intended application. In embodiments, the viscosity of the curable composition may be from about 0.2 to about 43 Pa·S, from about 1 to about 35 Pa·S, from about 5 to about 25 Pa·S, or even from about 10 to about 20 Pa·S.

[0100] The curable organosilicon composition of the present invention can be cured to obtain a cured product with high hardness and excellent transparency, crack resistance and heat resistance. The curing conditions are not particularly limited and vary depending on the amount of composition, but the curing temperature is preferably within the range of 60 to 180°C, and the curing time is typically within the range of 0.5 to 10 hours. In an embodiment, curing can be achieved in 30 minutes at a temperature of about 100°C. Curing can also be achieved by UV curing, which is carried out according to the standard procedure of exposure to UV radiation.

[0101] The cured materials formed from the curable compositions may also exhibit desirable properties for various applications. In embodiments, the curable compositions may have a refractive index greater than about 1.40. In embodiments, the curable compositions have a refractive index of about 1.40 to about 1.60; about 1.42 to about 1.58; or even 1.45 to about 1.50.

[0102] The cured material may also exhibit excellent optical clarity, in embodiments, a 1 mm thick sheet of the cured material has a transparency of about 95% or greater, about 96% or greater, about 97% or greater, about 98% or greater, or even about 99% or greater from 400 nm to about 800 nm.

[0103] The cured materials may also exhibit high thermal stability and crack resistance, which are evaluated and understood in terms of a variety of accepted test methods, including but not limited to adhesion after water immersion, limit strain, abrasion, microindentation testing, etc.

[0104] The cured material may also exhibit good water vapor permeability. In an embodiment, a 1 mm thick sheet of the cured material has a water vapor permeability of about 0.1 to about 15 g / m2 according to the JIS Z0208 test method. 2 This is also called the water vapor transmission rate, water vapor transmission rate, or oxygen transmission rate (MVTR, WVTR, or O-transmission rate). The water vapor transmission rate, water vapor transmission rate, or oxygen transmission rate ranges from about 0.1 to about 15 g / m 2 Days: 0.5 to 10g / m 2 1 to 7.5 g / m per day 2 Days: approx. 2 to 5 g / m 2In one embodiment, the water vapor transmission rate, water vapor transmission rate, and oxygen permeability can be from about 10 to about 15 g / m 2 Here, as elsewhere in the specification and claims, numerical values ​​may be combined to form new, undisclosed ranges.

[0105] The curable organosilicon composition of the present invention is useful as a curable silicone material, an encapsulant for optical devices such as optical elements, an encapsulant for other electronic devices such as semiconductor elements, and an electrically insulating coating material. Examples of optical devices include optical elements such as LEDs, semiconductor lasers, photodiodes, phototransistors, solar cells, and CCDs; and optical parts such as lenses, bonding materials, adhesives, films, and sheets. The cured material may be used as an encapsulant, for example, an LED encapsulant. Examples of electronic devices include semiconductor elements such as diodes, transistors, ICs, CPUs, and memory elements.

[0106] The curable silicone composition can be included in personal care compositions such as, but not limited to, cosmetics, sunscreens, hair products such as shampoos or conditioners, lotions, creams, etc. The personal care composition can include a variety of ingredients such as carriers, pigments, film formers, emulsifiers, vitamins, plasticizers, surfactants, antioxidants, waxes, oils, solvents, etc.

[0107] In one embodiment, the personal care product may optionally contain 0 to 90 parts by weight of pigment. Pigments suitable for use herein are all inorganic and organic colorants / pigments. These are typically aluminum, barium or calcium salts or lakes. Lakes are pigments extended or reduced with solid diluents or organic pigments prepared by precipitating a water-soluble dye onto an adsorbent surface, usually an aluminum hydrate. Lakes are also formed from the precipitation of insoluble salts from acid or basic dyes. Calcium and barium lakes are also used herein. Suitable lakes include, but are not limited to, Red 3 aluminum lake, Red 21 aluminum lake, Red 27 aluminum lake, Red 28 aluminum lake, Red 33 aluminum lake, Yellow 5 aluminum lake, Yellow 6 aluminum lake, Yellow 10 aluminum lake, Orange 5 aluminum lake and Blue 1 aluminum lake, Red 6 barium lake, Red 7 calcium lake. Other colorants and pigments such as pearl, titanium dioxide, Red 6, Red 21, Blue 1, Orange 5 and Green 5 dyes, chalk, talc, iron oxide, and titanated mica may also be included in the composition.

[0108] The personal care composition may optionally contain 0 to 99 parts by weight of an organic film former known in the art. The film former may be any cosmetically acceptable one. Examples of useful film formers include natural waxes, polymers such as polyethylene polymers, and copolymers of PVP, ethylene vinyl acetate, dimethicone gum, and resins such as shellac, polyterpene, etc.

[0109] The personal care composition may optionally contain 0-50 parts by weight of either a blocking or absorbing sunscreen. Blocking sunscreens are generally inorganic, such as various cesium oxides, chromium oxides, cobalt oxides, iron oxides, red petrolatum, silicone-treated and other treated titanium dioxides, titanium dioxide, zinc oxide, and / or zirconium oxides, BaTiO3, CaTiO3, SrTiO3, and SiC. Absorbing screening agents, which are usually organic, are particularly useful. Such absorbing sunscreens include, but are not limited to, UV-A absorbers, which generally absorb radiation in the 320 to 400 nm region of the ultraviolet spectrum, such as anthranilates, benzophenones, and dibenzoylmethanes; and UV-B absorbers, which generally absorb radiation in the 280 to 320 nm region of the ultraviolet spectrum, such as p-aminobenzoic acid derivatives, camphor derivatives, cinnamates, and salicylates. Specific examples of organic sunscreens include p-aminobenzoic acid, avobenzone cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octocrylene, octyl methoxycinnamate, octyl salicylate, oxybenzone, padimate, phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate, aminobenzoic acid, amyl dimethyl p-aminobenzoate, diethanolamine p-methoxycinnamate, digalloyl trioleate, 2-Ethylhexyl-2-cyano-3,3-diphenylacrylate, Ethylhexyl p-methoxycinnamate, 2-Ethylhexyl salicylate, Glyceryl aminobenzoate, Homomenthyl salicylate, Homosalate, 3-Imidazol-4-ylacrylic acid and its ethyl ester, Methyl anthranilate, Octyl dimethyl PABA, 2-Phenylbenzimidazole-5-sulfonic acid and salts, Sulisobenzone, Triethanolamine salicylate, N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl)anilinium methylsulfate, aminobenzoate, 4-isopropylbenzyl salicylate, 2-ethylhexyl 4-methoxycinnamate, methyl diisopropylcinnamate, isoamyl 4-methoxycinnamate, diethanolamine 4-methoxycinnamate, 3-(4'-trimethylammonium)-benzylidene-boman-2-one methylsulfate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzo Phenone-5-sulfonate, 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-4'-methoxybenzophenone, ca-(2-oxoborn-3-ylidene)-tolyl-4-sulfonic acid and its soluble salts, 3-(4'-sulfo)benzylidene-bornan-2-one and its soluble salts, 3-(4'-methylbenzylidene)- d,l-camphor, 3-benzylidene-d,l-camphor, benzene 1,4-di(3-methylidene-10-camphorsulfonic) acid and its salts, urocanic acid, 2,4,6-tris-(2'-ethylhexyl-1'-oxycarbonyl)-anilinol 1,3,5-triazine, 2-(p-(tert-butylamido)anilinol-4,6-bis-(p-(2'-ethylhexyl 1'-oxycarbonyl)anilinol 1,3,5-triazine, 2,4-bis{1,4-(2-ethylhexyloxy)-2-hydroxyl- phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, polymers of N-(2et4)-(2-oxoborn-3-ylidene)methylbenzyl acrylamide, 1,4-bisbenzimidazolyl-phenylene-3,3',5,5'-tetrasulfonic acid and its salts, benzalmalonate-substituted polyorganosiloxanes, benzotriazole-substituted polyorganosiloxanes (drometrizole trisiloxanes), solubilized 2,2'-methylene-bis-1,6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane, and combinations comprising at least one of the above sunscreens.

[0110] The personal care composition may be specially formulated for use as, but not limited to, color cosmetics, sunscreens, hair conditioners, moisturizers, and the like. Forms and formulations suitable for such uses are known to those skilled in the art. For example, when formulated for use as a sunscreen, the composition may be in the form of a lamellar emulsion, a microemulsion, or a nanoemulsion. Furthermore, the emulsion may be a fluid simple emulsion, a fluid multiple emulsion, a rigid simple emulsion, or a rigid multiple emulsion. The simple emulsion or multiple emulsion may include a continuous aqueous phase with dispersed lipid vesicles or oil droplets, or a continuous fatty phase with dispersed lipid vesicles or aqueous droplets. In one embodiment, the sunscreen application is an emulsion with a continuous aqueous phase, and may be in the form of a stick, lotion, gel, spray, and the like. Emulsifiers suitable for forming sunscreen emulsions include, for example, ethoxylated surfactants known in the art, such as Polysorbate-20, Laureth-7, Laureth-4, Sepigel® 305 from SEPPIC, oils such as vegetable oils and mineral oils; animal and / or synthetic waxes such as beeswax, paraffin, rice bran wax, candelilla wax, carnauba wax and derivatives thereof; and hydrocarbon gels or bentonite type gels such as Gel SS71, Gel EA2786, Quaternium-18 Bentonite, 38 CE, Gel ISD V or Gel ISD; and Cetyl Dimethicone Copolyol-Polyglyceryl 4-Isostearate-Hexyl Laurate (ABIL® WE 09), Behenate Dimethicone, Cetyl Dimethicone Copolyol (ABIL® EM 90), (ABIL® EM 100), available from Goldschmidt Chemical Corporation. 97), Lauryl Methicone Copolyol (5200), Cyclomethicone and Dimethicone Copolyol (DC 5225 C and DC 3225 C), Cyclopentasiloxane and Dimethicone Copolyol (SF 1528).

[0111] The personal care composition may optionally include vitamins or skin nutrients. Some suitable agents are ceramides, hyaluronic acid, panthenol, peptides (copper hexapeptide-3), AHA (lactic acid), retinol (retinyl palmitate) - vitamin A derivative, vitamin C (l-ascorbic acid), BHA (salicylic acid), tea (green, white, black), soy and other plant derivatives, isoflavones (grape seed extract), argireline, acai berry.

[0112] Plasticizers can also be added to the formulation to improve the flexibility and cosmetic properties of the resulting formulation. Plasticizers are frequently used to avoid brittleness and cracking of film formers, and include, for example, lecithin, polysorbates, dimethicone copolyols, glycols, citrate esters, glycerin, and dimethicone. Those skilled in the art can routinely vary the amount of plasticizer required based on the desired properties and the intended use.

[0113] The compositions of the present invention can be incorporated into a carrier, such as a volatile carrier that volatilizes quickly after application. The volatile carrier can be selected from volatile hydrocarbons, volatile silicones, and mixtures thereof.

[0114] Hydrocarbon oils useful in personal care products include those having from about C8 to about C 20 Chain length, and also C8 to C 20 Included among the hydrocarbon oils having isoparaffins are those having boiling points in the range of 60-260° C. Examples include isododecane, isohexadecane, isoeocosane, 2,2,4-trimethylpentane, 2,3-dimethylhexane, and mixtures of two or more thereof.

[0115] Suitable volatile silicone fluids include those having the formula (RSiO): x where x is from about 3 to about 6.

[0116] The above includes examples of the present specification. Of course, it is not possible to describe every conceivable combination of components or methodologies for purposes of describing the present specification, but one skilled in the art will recognize that many further combinations and variations of the present specification are possible. Therefore, the present specification is intended to embrace all such changes, modifications, and variations that are within the spirit and scope of the appended claims. Furthermore, to the extent that the term "comprises" is used in either the detailed description or the claims, such term is intended to be inclusive in a manner similar to the term "comprises" as it would be interpreted if "comprises" were used as a transitional phrase in a claim. EXAMPLES

[0117] Aspects of the present disclosure will now be described and can be further understood with reference to the following examples, which are to be understood as being for illustrative purposes only and are not intended to limit the invention disclosed herein with respect to materials, or process parameters, equipment, or conditions.

[0118] Example 1: Preparation of component (A-1) Component A-1 can be made according to the following procedure.

[0119] A norbornene end-capped phenylmethylsilicone norbornenylethyl block copolymer (A-1) having a molecular weight of 3 kD was synthesized according to the following scheme:

[0120] In a 500 mL three-necked round bottom flask under nitrogen environment equipped with a reflux condenser, dropping funnel and mechanical stirrer, 100 mL of toluene and 5-vinylbicyclo[2.2.1]hept-2-ene (128.7 g, 1.07 mol) were added. To this solution, 0.289 g of Karstedt's catalyst (15 ppm of 2 wt% Pt) was added. The entire setup was kept in an oil bath while maintaining the reaction temperature at 50 °C. 3-Phenyl-1,1,3,3,5-pentamethyltrisiloxane (257.51 g, 0.95 mol) in the dropping funnel was added dropwise over 1 h. The reaction temperature was then increased to 80 °C and continued until all the hydride was consumed. After completion of the hydrosilylation polymerization, unreacted starting materials, volatile compounds and solvents were removed under reduced pressure. The final product was obtained as a yellow liquid in quantitative yield, which was decolorized with activated carbon to give the desired product as a colorless liquid in quantitative yield (viscosity at 25° C.: 6810 mPa.s; GPC: M n =3.06kD;M w = 4.6 kD; PDI = 1.5). [ka]

[0121] A norbornene end-capped phenylmethylsilicone norbornenylethyl block copolymer having a molecular weight of 140 kD (Component A-2) was synthesized similarly to the method described for A-1.

[0122] Briefly, 150 mL of toluene and 5-vinylbicyclo[2.2.1]hept-2-ene (94 g, 0.78 mol) were added to a 500 mL three-neck round bottom flask. To this solution, 0.225 g of Karstedt catalyst (15 ppm of 2 wt% Pt) was added. 3-Phenyl-1,1,3,3,5-pentamethyltrisiloxane (200 g, 0.74 mol) in a dropping funnel was added dropwise to the reaction mixture at 50 °C over 1 h. Then, the reaction temperature was increased to 80 °C and continued until all the hydride was consumed. After completion of the hydrosilylation polymerization, the unreacted starting materials, volatile compounds and solvent were removed under reduced pressure. The final product was obtained as a yellow liquid in quantitative yield and was decolorized with activated carbon to obtain the desired product as a colorless liquid in quantitative yield (viscosity at 25 °C: 14200 mPa.s; GPC: M n =5.2kD;M w = 7.8 kD; PDI = 1.5). [ka]

[0123] Example 2: Ingredient (A-2) The compound of the following formula is provided as component A-2: [ka]

[0124] Example 3-10: Curable composition Example 3

[0125] A curable silicone composition was prepared by mixing 43.85 parts by weight of A1, 41.5 parts by weight of polyisobutene (Olissopal 1000), 0.025 parts by weight of platinum-vinylsiloxane complex as a curing catalyst, and 0.125 parts by weight of diallyl maleate as a reaction inhibitor. Subsequently, 14.5 parts by weight of polyferryl-idemethylhydrosiloxy)siloxane crosslinker was added to the resulting mixture. The composition was thoroughly mixed with a high-speed mixer until a uniform distribution of the components was achieved. The composition was then poured into a mold formed from a glass plate to produce a thickness of 1 mm, and then heated at 150 ° C for 2 hours to obtain a cured product.

[0126] Example 4

[0127] A curable silicone composition was prepared by mixing 26.75 parts by weight of siloxane component A1, 63.6 parts by weight of polyisobutene (Olissopal 1000), 0.025 parts by weight of platinum-vinylsiloxane complex catalyst, and 0.125 parts by weight of diallyl maleate as a reaction inhibitor. Subsequently, 9.5 parts by weight of polyferryl-idemethylhydrosiloxy)siloxane as a crosslinking agent component was added to the resulting mixture. The entire composition was thoroughly mixed with a high-speed mixer until a uniform distribution of the components was achieved. The composition was then poured into a mold formed from a glass plate to produce a thickness of 1 mm, and then heated at 150° C. for 2 hours to obtain a cured product.

[0128] Example 5

[0129] The curable silicone composition was prepared by mixing 33.5 parts by weight of A1, 60 parts by weight of polyisobutene (Olissopal 1000), 0.025 parts by weight of platinum-vinylsiloxane complex catalyst, and 0.125 parts by weight of diallyl maleate as a reaction inhibitor. Subsequently, 6.35 parts by weight of polyferryl-idemethylhydrosiloxy)siloxane as a crosslinking agent component was added to the resulting mixture. The entire composition was thoroughly mixed with a high-speed mixer until a uniform distribution of the components was achieved. The composition was then poured into a mold formed from a glass plate to produce a thickness of 1 mm, and then heated at 150° C. for 2 hours to obtain a cured product.

[0130] Example 6

[0131] A curable silicone composition was prepared by mixing 25.9 parts by weight of A1, 60 parts by weight of polyisobutene (Olissopal 1000), 0.025 parts by weight of platinum-vinylsiloxane complex catalyst, and 0.125 parts by weight of diallyl maleate as a reaction inhibitor. Subsequently, 10.35 parts by weight of a hydride-modified MQ resin (MQH-9) as a crosslinking agent component was added to the resulting mixture. The entire composition was thoroughly mixed in a high-speed mixer until a uniform distribution of the components was achieved. The composition was then poured into a mold formed from a glass plate to produce a thickness of 1 mm, and then heated at 150° C. for 2 hours to obtain a cured product.

[0132] Example 7

[0133] A curable silicone composition was prepared by mixing 29.9 parts by weight of copolymer A-2, 59.9 parts by weight of multiacrylate (Ebecryl 745), 5 parts by weight of isobornyl acrylate, and 5 parts by weight of 2-ethylhexyl acrylate. 0.2 parts by weight of a radiation curable initiator was then added to the resulting mixture. The entire composition was thoroughly mixed in a high speed mixer until a uniform distribution of the components was achieved. The composition was then poured into a mold and exposed to ultraviolet light (metal halide, 3000 mJ / cm2). 2 ) to form a cured product 1 mm thick.

[0134] Example 8

[0135] A curable composition was prepared by adding 59.9 parts by weight of copolymer A-2, 29.9 parts by weight of multiacrylate (Ebecryl 745), 10 parts by weight of isobornyl acrylate and 0.2 parts by weight of radiation curable initiator, similar to the composition shown in Example 7. The composition was cured under UV irradiation to obtain a 1 mm cured sheet.

[0136] Example 9

[0137] A curable composition was prepared by adding 49.9 parts by weight of copolymer A-2, 9.9 parts by weight of multiacrylate (EM221), 20 parts by weight of isobornyl acrylate, 20 parts by weight of 2-ethylhexyl acylate, and 0.2 parts by weight of a radiation curable initiator, similar to the composition shown in Example 7. 1 mm cured sheets were obtained by curing the composition under UV light as described above in Example 8.

[0138] Example 10

[0139] A curable composition was prepared by adding 39.9 parts by weight of copolymer A-2, 49.9 parts by weight of C1, 10 parts by weight of isobornyl acrylate, and 0.2 parts by weight of a radiation curable initiator, similar to the composition shown in Example 4. 1 mm cured sheets were obtained by curing the composition under UV light as described above in Example 8.

[0140] Performance evaluation The properties of the cured sheets obtained from the examples were evaluated (1 mm) by the following methods. The results are summarized in Table 1. [Table 1]

[0141] The viscosity of the curable compositions was measured using a HAAKE RheoStress 600 at 25°C.

[0142] The cured sheets of each example were visually inspected to obtain appearance information.

[0143] The clarity of the cured sheets was measured spectrophotometrically (Gretag Macbeth Color Eye7000A Spectrophotometer).

[0144] The water vapor permeability (WVTR) of the cured articles was evaluated according to method JIS Z 0208 using a permeability cup tester manufactured by Yasuda Seiki Seisakusho. [Table 2]

[0145] The cured products obtained from the curable compositions exhibited excellent properties, as shown in Table 2. The products were colorless and transparent and also showed a high degree of flexibility. Furthermore, the products also showed resistance to coloration when exposed to heat and light, indicating their applicability in optoelectronic applications as encapsulants and barrier adhesives.

[0146] The foregoing description identifies various non-limiting embodiments of the heater assembly. Modifications may occur to those skilled in the art and those able to make and use the invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or the subject matter described in the claims.

Claims

1. (A) an organopolysiloxane having the following formula: 【Chemistry 1】 Here, R １ are cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1,1-diethenylcyclohexane; 1,3-diethenylcyclohexane; bicyclo[2.2.1]-2,5-diethenylheptane; 1,4-di-2-prop-1-ylcyclohexane; 1,3-diisopropenylbenzene; spiro[5.5]-3,8-diethenylundecane; 1,3-diethenyl adamantane; vinylnorbornene; 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane; pinane, bornane, norpinane, norbornane, spiro[2.2]pentane, spiro[2.3]hexane, spiro[2.4]heptane, spiro[2.5]octane, spiro[3.3]heptane, spiro[3.4]octane, spiro[3.5]nonane, spiro[4.4]nonane, Spiro[4.5]decane, spiro[5.5]undecane, bicyclo[1.1.0]butane, bicyclo[2.1.0]pentane, bicyclo[2.2.0]hexane, bicyclo[3.1.0]hexane, bicyclo[3.2.0]heptane, bicyclo[3.3.0]octane, bicyclo[4.1.0]heptane, bicyclo[4.2.0]octane, bicyclo[4.3.0]nonane, bicyclo[4.4.0]decane cane, bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.1.1]heptane, bicyclo[3.2.1]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, bicyclo[3.3.2]decane, bicyclo[3.3.3]undecane, adamantyl, tricyclo[5.2.1.0 ２，６ ]decane or tricyclo[4.3.1.1 ２，５ ] is selected from divalent groups containing a C4-C30 cyclic-containing hydrocarbon group selected from an undecane ring; R ２ is a curable functional group independently selected from vinyl, vinyl-containing groups, unsaturated hydrocarbons, unsaturated cyclic hydrocarbons, acrylates, methacrylates, hydroxys, alkoxys, and epoxy; R ３ -R １４ are independently selected from hydrogen, a C1-C10 monovalent hydrocarbon group, a C6-C20 monovalent aromatic group, and a C4 to C30 monovalent saturated or unsaturated cycloalkyl group, a siloxy group containing from 1 to 20 silicon atoms; x and z are independently 1 to 30; y and w are independently 0-30; and n is 1-30; and (B) a silicone-free, curable silicone composition comprising an organic material that includes reactive functional groups.

2. 2. The curable composition of claim 1, wherein said silicone-free organic material (B) is selected from ethylenically unsaturated monomers, ethylenically unsaturated aromatic compounds, ethylenically unsaturated acids, ethylenically unsaturated anhydrides, acrylates, methacrylates, acrylamides, or combinations of two or more thereof.

3. 3. The curable silicone composition of claim 1 or 2, wherein said silicone-free organic material (B) is selected from an organic monomer containing an olefinic functionality, an organic monomer containing an acrylic functionality, an organic oligomer containing an acrylic functionality, or a combination of two or more thereof.

4. The curable composition of claim 3, wherein said monomer is selected from polyisobutenes containing alkenyl functionality.

5. The curable composition of claim 4, wherein said polyisobutene is selected from vinyl-terminated polyisobutenes.

6. 3. The curable composition of claim 2, wherein the organic monomer (B) is an organic monomer containing an acrylic functionality selected from an alkyl acrylate, an alkylene glycol acrylate, an epoxy acrylate, an alkoxylated epoxy acrylate, an alkoxyalkyl acrylate, an aryl acrylate, a urethane acrylate, an aminated acrylate, or a combination of two or more thereof.

7. The organic monomers containing an acrylic functional group include 2-butoxyethyl acrylate, 2-butoxyethyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-ethyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-hydroxyethyl acrylate, 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, benzyl acrylate, cyclohexyl acrylate, di(ethylene glycol)ethyl ether acrylate, di(ethylene glycol)ethyl ether methacrylate, di(ethylene glycol)methyl ether methacrylate, dicyclofentanyl acrylate, epoxy acrylate, ethylene glycol methyl ether acrylate, ethylene glycol phenyl ether acrylate, hydroxypropyl acrylate, isobornyl acrylate, methyl adamantyl acrylate, neopentyl glycol benzoate acrylate, 2-hydroxymethyl methacrylate, adamant ...

7. The curable composition of claim 6, wherein the curable acrylate is selected from the group consisting of butyl methacrylate, alkyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, epoxycyclohexylmethyl methacrylate, ethylene glycol phenyl ether methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, methyl adamantyl methacrylate, methyl methacrylate, methyl glycidyl methacrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, alkyl acrylates, 2-hydroxyacrylates, trimethoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3-fluoroethyl acrylate, 4-fluoropropyl acrylate, and triethylsiloxylethyl acrylate, or a combination of two or more thereof.

8. R ２ is selected from a C1-C20 hydrocarbon radical containing a vinyl functionality, a monovalent C4-C20 branched hydrocarbon radical containing a vinyl functionality, or a monovalent C4-C30 cyclic hydrocarbon radical containing a vinyl functionality.

9. R ２ is the formula X-R １６ -, where X is a vinyl group (CH ２ =CH ２ -), non is a curable functional group selected from a saturated cyclic group and an unsaturated polycyclic group, and R １６ The curable silicone composition of any of claims 1-8, wherein is a bond or a C1-C20 divalent hydrocarbon radical.

10. X is cyclopentene, cyclohexene, cyclooctene, pinene, bornene, norpinene, norbornene, spiro[2.2]pentene, spiro[2.3]hexene, spiro[2.4]heptene, spiro[2.5]octene, spiro[3.3]heptene, spiro[3.4]octene, spiro[3.5]nonene, spiro[4.4]nonene, spiro[4.5]decene, spiro[5.5]undecene, bicyclo[1.1.0]butene, bicyclo[2.1.0]pentene, bicyclo[2.2.0]hexene, bicyclo[3.1.0]hexene, bicyclo[3.2.0]heptene, Bicyclo[3.3.0]octene, bicyclo[4.1.0]heptene, bicyclo[4.2.0]octene, bicyclo[4.3.0]nonene, bicyclo[4.4.0]decene, bicyclo[1.1.1]pentene, bicyclo[2.1.1]hexene, bicyclo[2.2.1]heptene, bicyclo[2.2.2]octene, bicyclo[3.1.1]heptene, bicyclo[3.2.1]octene, bicyclo[3.2.2]nonene, bicyclo[3.3.1]nonene, bicyclo[3.3.2]decene, bicyclo[3.3.3]undecene, adamantene, tricyclo[5.2.1.0 ２，６ ]decene, tricyclo[4.3.1.1 ２，５ 10. The curable silicone composition of claim 9, wherein the alkyl group is selected from the group consisting of 4-vinylcyclohexyl, 5-vinyl-2-propene, 4-vinyl-1, 4-vinyl-1-propene, 5 ...

11. The curable silicone composition of any of claims 1-10, further comprising: (C) a crosslinking agent; (D) a reaction accelerator; (E) an inhibitor; and / or (F) one or more additives.

12. 12. The curable silicone composition of claim 11, comprising a crosslinker (C), wherein the crosslinker is selected from a silicone-containing compound containing at least one -SiH group, at least one -SH group, a vinyl group, a vinyl-containing group, an unsaturated hydrocarbon, an unsaturated cyclic hydrocarbon, an acrylate, a methacrylate, a hydroxy, an alkoxy, an epoxy, or a combination of two or more thereof.

13. 13. The curable silicone composition of claim 11 or 12, wherein the reaction accelerator is selected from a photoinitiator, a thermal initiator, a metal-containing catalyst, or a combination of two or more thereof.

14. 14. The curable silicone composition of any of claims 11-13, wherein the inhibitor is selected from ethylenically unsaturated amides, aromatic unsaturated amides, acetylenic compounds, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon monoesters of unsaturated acids, conjugated or isolated ene-ynes, hydroperoxides, ketones, sulfoxides, amines, phosphines, phosphites, nitrites, diaziridines, or combinations of two or more thereof.

15. 15. The curable silicone composition of any of claims 11-14, wherein the additive is selected from antioxidants, heat stabilizers, adhesion promoters, fillers, pigments, dyes, filler treating agents, plasticizers, spacers, extenders, biocides, stabilizers, flame retardants, surface modifiers, anti-aging additives, rheology additives, corrosion inhibitors, surfactants, or combinations of two or more thereof.

16. 16. The composition of claim 15, wherein the adhesion promoter is selected from an aminosilane, an epoxysilane, an isocyanurate silane, a mercaptosilane, an imidosilane, an anhydride silane, a carboxylate-functionalized siloxane, or a combination of two or more thereof.

17. The curable silicone composition of any of claims 1-16, wherein the composition has a refractive index of from 1.40 to 1.

60.

18. The curable silicone composition of any of claims 1-17, wherein the composition has a transparency of 95% or greater.

19. The composition is －１ to 10 g / m ２ The curable silicone composition of any of claims 1-18, having an MVTR, WVTR, and O permeability of 1000 nm.

20. A cured article formed by curing the composition of any of claims 1-19.

21. The article has a refractive index of 1.40 to 1.60; a transparency of 95% or greater; －１ to 10 g / m ２ 21. The cured article of claim 20, having an MVTR, WVTR, O permeability, or a combination of two or more thereof, of -1.

22. 22. The cured article of claim 20 or 21, wherein the article is selected from an encapsulant, an optical waveguide, a lens, a bonding material, an adhesive, a film or sheet, a laminated film of sheets, a coating, a pressure sensitive adhesive, a wound care patch.

23. 23. The cured article of any of claims 20-22, wherein the article is selected from an LED encapsulant, a light guide, an optical lens, an optical bond, an optical adhesive, an optical film or sheet, a laminate of sheets in combination with an electronic component or semiconductor device.

24. A personal care composition comprising the curable silicone composition of any of claims 1-19.

25. 25. The personal care composition of claim 24, wherein the personal care composition is selected from a cosmetic formulation, a sunscreen, a shampoo, a conditioner, a lotion, or a cream.

26. 20. A method of forming a cured article comprising subjecting the composition of any of claims 1-19 to conditions of heating and / or UV irradiation to effect curing of said composition.

27. A compound of the formula: 【Chemistry 2】 Here, R ３ , R ４ , R ６ , R ７ , R ８ , R ９ , R １０ , R １２ , R １３ , and R １４ is a methyl group, R ５ and R １１ is a phenyl group; R １ contains a bicyclo[2.2.1]heptane group; R ２ contains a methacrylate group; x and z are independently 1 to 30; y and w are independently 1 to 30; and The compound wherein n is 1-30.

28. The compound is of the formula: 【Chemistry 3】 The compound of claim 27, wherein n is 1-29.

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